Silica film forming material, silica film and method of manufacturing the same, multilayer wiring structure and method of manufacturing the same, and semiconductor device and method of manufacturing the same

ABSTRACT

The silica film forming material of the present invention comprises a silicone polymer which comprises, as part of its structure, CHx, an Si—O—Si bond, an Si—CH 3  bond and an Si—CHx- bond, where x represents an integer of 0 to 2.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefits of the priorityfrom the prior Japanese Patent Application No. 2005-200967, filed onJul. 8, 2005, the entire contents of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a silica film forming material suitablefor a multilayer wiring structure in a semiconductor integrated circuit,a silica film formed by using the silica film forming material and amethod of manufacturing the same, a multilayer wiring structure and amethod of manufacturing the same, and a semiconductor device comprisingthe silica film as an interlayer insulation film or a protection filmand a method of manufacturing the same.

2. Description of the Related Art

With the increase in the level of integration of semiconductorintegrated circuits and the improvement of element density in recentyears, the demand for higher lamination semiconductor integratedcircuits is especially rising. With the trend for higher integratedsemiconductor circuits, the space between wirings is becoming narrower,which is creating the problem of a wiring delay due to an increase ininter-wiring capacity. Here, the wiring delay (T) is expressed as thefollowing formula: T∝CR, and is affected by the wiring resistance (R)and the inter-wiring capacity (C). Furthermore, the relationship betweenthe dielectric constant (∈) and the inter-wiring capacity (C) isexpressed with the following equation: C=∈₀∈_(r)·S/d, where S is anelectrode area, ∈₀ is a electric constant, ∈_(r) is a dielectricconstant of the insulation film, and d is a space between the wirings,respectively. The inter-wiring capacity (C) may be decreased by makingthe wiring thickness to be thinner to reduce the electrode area, butmaking the wiring thickness thinner causes a further rise in the wiringresistance (T), which in turn prevents the achievement of higher speed.Hence, lowering the dielectric constant of the insulation film becomesan effective method for minimizing the wiring delay (T) and achievinghigher speed.

With an increase in the level of the integration of the semiconductorintegrated circuit and the improvement in element density in recentyears, a space between metal wirings tends to become narrow in asemiconductor device having a multilayer wiring structure. Hence, theimpedance of the metal wiring due to static electricity induction isrising, leading to concern that the response speed may be delayed andelectric consumption is growing. For this reason, it becomes crucial tomake the relative dielectric constant of the interlayer insulation filmprovided between the semiconductor substrate and the metal wiring layeror between the metal wiring layers to be as small as possible.

Example of conventional material of the insulation film is an inorganicmaterial such as a silicon dioxide (SiO₂), a silicon nitride (SiN), anda phospho-silicate glass (PSG), or an organic polymer material such as apolyimide. However, the dielectric constant of CVD-SiO₂ film frequentlyused in semiconductor device is high at around 4. Moreover, SiOF film,which is considered to be used as low dielectric constant CVD film, hasa dielectric constant of about 3.3 to 3.5, but it has the problem ofhigh moisture absorption properties that result in a rising dielectricconstant over time. Moreover, porous silica film having low dielectricconstant has been proposed (See Japanese Patent Application Laid-Open(JP-A) No. 2004-153147). The method of manufacturing such a porous filmenables further lowering of the dielectric constant because the methodcontains a process in which the heat-degradable components are heatedand degraded to form pores.

However, in the case of porous film of the siloxane resin, etchingprocessing is difficult due to the properties of such a porous film,hence formation of plasma CVD film such as SiCH with a dielectricconstant of about 4.5 in order to protect the film is required. Thispresents a problem in which the low dielectric constant properties ofthe porous film cannot be utilized effectively. Moreover, in formingfine wirings of 0.1 μm or less, an insulation film hard mask, athree-layered resist or the like is applied, which presents a problem inwhich the short of wirings or the leak current through the insulationfilm is created due to the impossibility of a high-degree of etchingselectivity relative to the porous film or protective film in a dryetching.

An objective of the present invention is to overcome the aforementionedproblems of the related art, and to achieve the following object. Infact, an object of the present invention is to provide: a silica filmwhich excels in properties of etching resistance, chemical resistance,and moisture resistance with superior adhesive properties and has a lowdielectric constant; a method of effectively forming the silica film; asilica film forming material suitable for forming the silica film; amultilayer wiring structure enabling lowering of the parasiticinter-wiring capacity; a method of effectively forming the multilayerwiring structure; a semiconductor device with high reliability and highspeed having the silica film as an interlayer insulation film orprotection film; and a method of effectively manufacturing thesemiconductor device.

SUMMARY OF THE INVENTION

The silica film forming material according to the present inventioncomprises a silicone polymer which comprises, as part of its structure,CHx, an Si—O—Si bond, an Si—CH₃ bond and an Si—CHx- bond, where xrepresents an integer of 0 to 2.

Preferably, the silicone polymer is obtained by a hydrolysiscondensation polymerization reaction of at least one of siliconcompounds expressed by the following general formulas (1) to (3), and atleast one of silicon compounds expressed by the following generalformulas (4) to (7):

where, in the general formulas (1) to (7), n represents either 0 or 1;R¹ may be the same as or different from each other, represents oneselected from the group consisting of a chlorine atom, a bromine atom, afluorine atom, and a hydrogen atom when n=0, and represents one selectedfrom the group consisting of a hydrocarbon with a carbon number of 1 to4, an aromatic hydrocarbon, a hydrogen atom and a carboxyl group whenn=1; R² represents one selected from the group consisting of ahydrocarbon with a carbon number of 1 to 4, an aromatic hydrocarbon, anda hydrogen atom; and R³ may be the same as or different from each other,and represents one selected from the group consisting of a hydrocarbonwith a carbon number of 1 to 3 and an aromatic hydrocarbon.

In the silica film forming material, the silicone compounds expressed bythe general formulas (1) to (3) each have excellent properties ofetching resistance, chemical resistance and moisture resistance, and thesilicone compounds expressed by the general formulas (4) to (7) eachhave excellent adhesion properties. Hence, silicone polymer obtained bythe hydrolysis condensation polymerization reaction of these siliconcompounds excels in all properties of the etching resistance, chemicalresistance, moisture resistance, and adhesion property, making thesilicone polymer suitable for use in the formation of a silica film andmultilayer wiring structure, which is ideal for various semiconductordevices. Moreover, the silicon polymer is especially suitable for use inthe formation of the silica covering film of the present invention,multilayer wiring structure of the present invention and thesemiconductor device of the present invention.

The method of manufacturing a silica film according to the presentinvention comprises: coating a silica film forming material on a surfaceto be processed; and heating the surface to be processed, wherein thesilica film forming material comprises a silicone polymer whichcomprises, as part of its structure, CHx, an Si—O—Si bond, an Si—CH₃bond and an Si—CHx- bond, where x represents an integer of 0 to 2. Inthe method of manufacturing a silica film, the silica film formingmaterial is coated onto the surface to be processed, and then heated.The result of which is the effective formation of the silica coveringfilm. The method of manufacturing a silica film is especially suitablefor the formation of the silica film of the present invention.

The silica film according to the present invention is formed by coatinga silica film forming material on a surface to be processed; and

heating the surface to be processed, wherein the silica film formingmaterial comprises a silicone polymer which comprise, as part of itsstructure, CHx, an Si—O—Si bond, an Si—CH₃ bond and an Si—CHx- bond,where x represents an integer of 0 to 2. Because it is formed with thesilica film forming material of the present invention, it has excellentproperties of etching resistance, chemical resistance and moistureresistance. Moreover, it has excellent adhesive properties with anunderlying layer. For this reason, it may be used as a hard mask duringa dry etching, simplifying the formation of a fine pattern. Further,because the adhesive properties are excellent even when the underlyinglayer has a small contact area, such as with porous film, separationfrom the underlying layer is prevented. Still further, because of a lowdielectric constant, the parasitic capacity is reduced, and the signaltransmission speed is improved, making it especially suitable for use ina high integration semiconductor integration circuit such as an IC andLSI in which higher response speeds are required.

The drop of the signal transmission speed due to the parasitic capacityof the insulation film has been known, but the effect of wiring delayson an overall device was small for generation in which the space betweenwirings of the semiconductor device is 1 μm or more. With the higherintegration and introduction of the multilayer wiring structure inrecent years, the wiring width and the space between the wirings arebecoming narrower, creating the problem of raising the wiring resistanceand increasing parasitic inter-wiring capacity, particularly when thespace of wirings is less than 1 μm. Because the signal transmissionspeed is determined in the multilayer wiring structure of thesemiconductor integration circuit by the wiring resistance and theparasitic inter-wiring capacity, which are major factors that controlperformance of the devices, such as the semiconductor integrationcircuit, the rise of wiring resistance and the increase in parasiticinter-wiring capacity are major problems to be overcome and are causesfor a drop in the signal transmission speed. In order to improve thesignal transmission speed, lowering the wiring resistance and decreasingthe parasitic inter-wiring capacity (dielectric constant of insulationfilm) are essential. The parasitic inter-wiring capacity may be reducedby making the wiring thinner to make the cross sectional-area smaller,but making the wiring thinner causes a rise in the wiring resistance. Inother words, lowering the parasitic inter-wiring capacity and decreasingthe wiring resistance are in an antinomic relationship, making itdifficult to improve the signal transmission speed. However, the silicafilm according to the present invention that may contribute to improvingthe response speed with a low dielectric constant enables lowering theparasitic inter-wiring capacity and a decrease in the wiring resistance,making it possible to improve the signal transmission speed.

The multilayer wiring structure according to the present inventioncomprises a silica film, wherein the silica film is formed by: coating asilica film forming material on a surface to be processed; and

heating the surface to be processed, and wherein the silica film formingmaterial comprises a silicone polymer which comprises, as part of itsstructure, CHx, an Si—O—Si bond, an Si—CH₃ bond and an Si—CHx- bond,where x represents an integer of 0 to 2. Because the silica film of thepresent invention with reduced parasitic capacity and a lower dielectricconstant is contained in the multilayer wiring structure, it is possibleto improve the signal transmission speed. Hence it is especiallysuitable for use in a semiconductor integration circuit in which higherresponse speeds are required.

The method of manufacturing a multilayer wiring structure according tothe present invention comprises: forming the silica film by coating asilica film forming material on a surface to be processed and by heatingthe surface to be processed; and forming a wiring, wherein the silicafilm forming material comprises a silicone polymer which comprises, aspart of its structure, CHx, an Si—O—Si bond, an Si—CH₃ bond and anSi—CHx- bond, where x represents an integer of 0 to 2. In the method ofmanufacturing a multilayer wiring structure, the silica film is formedby coating the silica film forming material and by heating the surfaceto be processed so as to form the silica film, and then, the wiring isformed. With repeated execution of the series of processes of forming asilica film and forming a wiring, the multilayer wiring structure of thepresent invention is efficiently formed. The method of manufacturing amultilayer wiring structure is especially suitable for the formation ofthe multilayer wiring structure of the present invention.

The semiconductor device according to the present invention comprises asilica film, the silica film being used as one of an interlayerinsulation film and a protection film formed on a surface of theinterlayer insulation film, wherein the silica film formed by: coating asilica film forming material on a surface to be processed; and heatingthe surface to be processed, and wherein the silica film formingmaterial comprises a silicone polymer which comprises, as part of itsstructure, CHx, an Si—O—Si bond, an Si—CH₃ bond and an Si—CHx- bond,where x represents an integer of 0 to 2. Because the semiconductordevice comprises the silica film of the present invention, both loweringof the parasitic inter-wring capacity and decreasing the wiringresistance are achieved, making it especially suitable for high speedand highly reliable flash memories, such as DRAM, FRAM, MOS transistorsand the like.

The method of manufacturing s semiconductor device according to thepresent invention comprises: forming a silica film on a surface to beprocessed, using a silica film forming material; and patterning thesurface to be processed by performing an etching, using the silica filmas a mask, wherein the silica film forming material comprises a siliconepolymer which comprises, as part of its structure, CHx, an Si—O—Si bond,an Si—CH₃ bond and an Si—CHx- bond, where x represents an integer of 0to 2. In the method of manufacturing a semiconductor device, first, thesilica film is formed using the silica film forming material on thesurface to be processed, which is a target on which the multilayerwiring structure is formed. Next, the surface to be processed ispatterned through an etching with the formed silica film as a mask. As aresult, both lowering of the parasitic inter-wiring capacity anddecreasing the wiring resistance are achieved, and a high performancesemiconductor with a higher signal transmission speed is efficientlymanufactured. The method of manufacturing a semiconductor device isespecially suitable for the method of manufacturing the semiconductordevice of the present invention.

Conventionally, the semiconductor device has been manufactured byforming a low dielectric constant insulation film (interlayer insulationfilm), forming a protective layer through a plasma CVD, and forming anetching stopper layer. However, such a manufacturing method requires theformation of an interlayer insulation film through reciprocation of avacuum chamber and a curing furnace, creating the problem of high cost.However, in the method of manufacturing a semiconductor device of thepresent invention, the silica film of the present invention is formed,making it possible to lower insulation film lamination cost and decreaseparasitic capacity through a lower dielectric constant, the result ofwhich is the achievement of an improvement in signal transmission speed.Moreover, because of excellent etching resistance, the silica film maybe used as a hard mask during a dry etching, enabling more efficientmanufacture of a semiconductor device with effective fine patternformation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1K are a process diagram showing an example of the method ofthe semiconductor device of the present invention containing the silicafilm of the present invention.

FIG. 2 is a graph showing the results of infrared spectrum analysis ofthe silica films obtained in the example and the comparative example.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(Silica Film Forming Material)

The silica film forming material according to the present inventioncontains at least a silicone polymer that has, as part of the structure,CHx, an Si—O—Si bond, an Si—CH₃ bond and an Si—CHx- bond, and an organicsolvent and other components as needed.

—Silicone Polymer—

It is necessary for the silicone polymer to contain CHx, an Si—O—Sibond, an Si—CH₃ bond and an Si—CHx- bond as part of its structure. Here,x represents an integer of 0 to 2. In this case, a silica film formingmaterial with excellent etching resistance, chemical resistance,moisture resistance and adhesiveness is obtained.

The method for verification of the presence of CHx, an Si—O—Si bond, anSi—CH₃ bond and an Si—CHx- bond in the silicone polymer is notparticularly limited, and may be appropriately selected according to theobject. In fact, containment of all of the structures may be confirmedthrough use of an infrared spectrum analyzer to measure the absorptionpeaks.

The silicone polymer is not particularly limited, and may beappropriately selected according to the object. Preferably, the siliconepolymer is obtained by the hydrolysis contraction polymerizationreaction of at least one of silicon compounds expressed by the followinggeneral formulas (1) to (3), and at least one of silicon compoundsexpressed by the following general formulas (4) to (7).

The silicon compounds expressed by the general following formulas (1) to(3) contain hydrocarbon or aromatic hydrocarbon in its skeleton, whichcan provide the silicone polymer with the properties such as etchingresistance, chemical resistance, moisture resistance and the like.Moreover, the silicon compounds expressed by the following generalformulas (4) to (7) can provide the silicone polymer with the propertiessuch as mechanical strength and adhesiveness with the underlying layer.

Here, in the general formulas (1) to (7), n represents either 0 or 1. R¹may be the same as or different from each other. When n=0, R¹ representsone selected from the group consisting of a chlorine atom, a bromineatom, a fluorine atom, and a hydrogen atom, and when n=1, R¹ representsone selected from the group consisting of a hydrocarbon with a carbonnumber of 1 to 4, an aromatic hydrocarbon, a hydrogen atom and acarboxyl group. R² represents one selected from the group consisting ofa hydrocarbon with a carbon number of 1 to 4, an aromatic hydrocarbon,and a hydrogen atom. R³ may be the same as or different from each other,and represents one selected from the group consisting of a hydrocarbonwith a carbon number of 1 to 3 and an aromatic hydrocarbon.

A combination of the silicon compounds to be used for the hydrolysiscontraction polymerization reaction varies with the value of n ingeneral formulas (1) to (7), but the following concrete combinations maybe provided depending on whether n is 1 or 0.

When n=1 in the general formulas (1) to (7), the combination of at leastone of the silicon compounds expressed by the following structuralformulas (1) to (3), and at least one of the silicon compounds expressedby the following structural formulas (4) to (7) may be suitably used.

Here, in the structural formulas (1) to (7), R¹ may be the same as ordifferent from each other, and represents one selected from the groupconsisting of a hydrocarbon with a carbon number of 1 to 4, an aromatichydrocarbon, a hydrogen atom, and a carboxyl group. R² represents oneselected from the group consisting of a hydrocarbon with a carbon numberof 1 to 4, an aromatic hydrocarbon, and a hydrogen atom. R³ may be thesame as or different from each other, and represents one selected fromthe group consisting of a hydrocarbon with a carbon number of 1 to 3 andan aromatic hydrocarbon.

The silicon compound expressed by the structural formula (1) is notparticularly limited, and may be appropriately selected according to theobject. Specific examples thereof include:

-   bis(trimethoxysilyl)methane,-   bis(triethoxysilyl)methane,-   1,2-bis(triethoxysilyl)ethane,-   1,3-bis(triethoxysilyl)propane,-   1,4-bis(triethoxysilyl)butane,-   1,4-bis(triethoxysilyl)benzene,-   bis(tripropoxysilyl)methane,-   1,2-bis(tripropoxysilyl)ethane,-   1,3-bis(tripropoxysilyl)propane,-   1,4-bis(tripropoxysilyl)butane,-   1,4-bis(tripropoxysilyl)benzene,-   bis(triisopropoxysilyl)methane,-   1,2-bis(triisopropoxysilyl)ethane,-   1,3-bis(triisopropoxysilyl)propane,-   1,4-bis(triisopropoxysilyl)butane,-   1,4-bis(triisopropoxysilyl)benzene,-   bis(tributoxysilyl)methane,-   bis(tri-tert-butoxysilyl)methane,-   1,2-bis(tri-tert-butoxysilyl)ethane,-   1,3-bis(tri-tert-butoxysilyl)propane,-   1,4-bis(tri-tert-butoxysilyl)butane,-   1,4-bis(tri-tert-butoxysilyl)benzene,-   bis(triacetoxysilyl)methane,-   1,2-bis(triacetoxysilyl)ethane,-   1,3-bis(triacetoxysilyl)propane,-   1,4-bis(triacetoxysilyl)butane,-   1,4-bis(triacetoxysilyl)benzene,-   bis(triphenoxysilyl)methane,-   1,2-bis(triphenoxysilyl)ethane,-   1,3-bis(triphenoxysilyl)propane,-   1,4-bis(triphenoxysilyl)butane,-   1,4-bis(triphenoxysilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (2) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include:

-   bis(dimethoxymethylsilyl)methane,-   1,2-bis(dimethoxymethylsilyl)ethane,-   1,3-bis(dimethoxymethylsilyl)propane,-   1,4-bis(dimethoxymethylsilyl)butane,-   1,4-bis(dimethoxymethylsilyl)benzene,-   bis(diethoxymethylsilyl)methane,-   1,2-bis(diethoxymethylsilyl)ethane,-   1,3-bis(diethoxymethylsilyl)propane,-   1,4-bis(diethoxymethylsilyl)butane,-   1,4-bis(diethoxymethylsilyl)benzene,-   bis(dipropoxymethylsilyl)methane,-   1,2-bis(dipropoxymethylsilyl)ethane,-   1,3-bis(dipropoxymethylsilyl)propane,-   1,4-bis(dipropoxymethylsilyl)butane,-   1,4-bis(dipropoxymethylsilyl)benzene,-   bis (diisopropoxymethylsilyl) methane,-   1,2-bis(diisopropoxymethylsilyl)ethane,-   1,3-bis(diisopropoxymethylsilyl)propane,-   1,4-bis(diisopropoxymethylsilyl)butane,-   1,4-bis(diisopropoxymethylsilyl)benzene,-   bis(dimethoxyethylsilyl)methane,-   1,2-bis(dimethoxyethylsilyl)ethane,-   1,3-bis(dimethoxyethylsilyl)propane,-   1,4-bis(dimethoxyethylsilyl)butane,-   1,4-bis(dimethoxyethylsilyl)benzene,-   bis(diethoxyethylsilyl)methane,-   1,2-bis(diethoxyethylsilyl)ethane,-   1,3-bis(diethoxyethylsilyl)propane,-   1,4-bis(diethoxyethylsilyl)butane,-   1,4-bis(diethoxyethylsilyl)benzene,-   bis(dipropoxyethylsilyl) methane,-   1,2-bis(dipropoxyethylsilyl)ethane,-   1,3-bis(dipropoxyethylsilyl)propane,-   1,4-bis(dipropoxyethylsilyl)butane,-   1,4-bis(dipropoxyethylsilyl)benzene,-   bis(diisopropoxyethylsilyl) methane,-   1,2-bis(diisopropoxyethylsilyl)ethane,-   1,3-bis(diisopropoxyethylsilyl)propane,-   1,4-bis(diisopropoxyethylsilyl)butane,-   1,4-bis(diisopropoxyethylsilyl)benzene,-   bis(dimethoxypropylsilyl)methane,-   1,2-bis(dimethoxypropylsilyl)ethane,-   1,3-bis(dimethoxypropylsilyl)propane,-   1,4-bis(dimethoxypropylsilyl)butane,-   1,4-bis(dimethoxypropylsilyl)benzene,-   bis(diethoxypropylsilyl)methane,-   1,2-bis(diethoxypropylsilyl)ethane,-   1,3-bis(diethoxypropylsilyl)propane,-   1,4-bis(diethoxypropylsilyl)butane,-   1,4-bis(diethoxypropylsilyl)benzene,-   bis(dipropoxypropylsilyl)methane,-   1,2-bis(dipropoxypropylsilyl)ethane,-   1,3-bis(dipropoxypropylsilyl)propane,-   1,4-bis(dipropoxypropylsilyl)butane,-   1,4-bis(dipropoxypropylsilyl)benzene,-   bis (diisopropoxypropylsilyl) methane,-   1,2-bis(diisopropoxypropylsilyl)ethane,-   1,3-bis(diisopropoxypropylsilyl)propane,-   1,4-bis(diisopropoxypropylsilyl)butane,-   1,4-bis(diisopropoxypropylsilyl)benzene,-   bis(dimethoxyisopropylsilyl)methane,-   1,2-bis(dimethoxyisopropylsilyl)ethane,-   1,3-bis(dimethoxyisopropylsilyl)propane,-   1,4-bis(dimethoxyisopropylsilyl)butane,-   1,4-bis(dimethoxyisopropylsilyl)benzene,-   bis(diethoxyisopropylsilyl) methane,-   1,2-bis(diethoxyisopropylsilyl)ethane,-   1,3-bis(diethoxyisopropylsilyl)propane,-   1,4-bis(diethoxyisopropylsilyl)butane,-   1,4-bis(diethoxyisopropylsilyl)benzene,-   bis(dipropoxyisopropylsilyl)methane,-   1,2-bis(dipropoxyisopropylsilyl)ethane,-   1,3-bis(dipropoxyisopropylsilyl)propane,-   1,4-bis(dipropoxyisopropylsilyl)butane,-   1,4-bis(dipropoxyisopropylsilyl)benzene,-   bis(diisopropoxyisopropylsilyl)methane,-   1,2-bis(diisopropoxyisopropylsilyl)ethane,-   1,3-bis(diisopropoxyisopropylsilyl)propane,-   1,4-bis(diisopropoxyisopropylsilyl)butane,-   1,4-bis(diisopropoxyisopropylsilyl)benzene,-   bis(dimethoxybutylsilyl)methane,-   1,2-bis(dimethoxybutylsilyl)ethane,-   1,3-bis(dimethoxybutylsilyl)propane,-   1,4-bis(dimethoxybutylsilyl)butane,-   1,4-bis(dimethoxybutylsilyl)benzene,-   bis(diethoxybutylsilyl)methane,-   1,2-bis(diethoxybutylsilyl)ethane,-   1,3-bis(diethoxybutylsilyl)propane,-   1,4-bis(diethoxybutylsilyl)butane,-   1,4-bis(diethoxybutylsilyl)benzene,-   bis(dipropoxybutylsilyl) methane,-   1,2-bis(dipropoxybutylsilyl)ethane,-   1,3-bis(dipropoxybutylsilyl)propane,-   1,4-bis(dipropoxybutylsilyl)butane,-   1,4-bis(dipropoxybutylsilyl)benzene,-   bis (diisopropoxybutylsilyl) methane,-   1,2-bis(diisopropoxybutylsilyl)ethane,-   1,3-bis(diisopropoxybutylsilyl)propane,-   1,4-bis(diisopropoxybutylsilyl)butane,-   1,4-bis(diisopropoxybutylsilyl)benzene,-   bis(dimethoxy-tert-butylsilyl) methane,-   1,2-bis(dimethoxy-tert-butylsilyl)ethane,-   1,3-bis(dimethoxy-tert-butylsilyl)propane,-   1,4-bis(dimethoxy-tert-butylsilyl)butane,-   1,4-bis(dimethoxy-tert-butylsilyl)benzene,-   bis(diethoxy-tert-butylsilyl)methane,-   1,2-bis(diethoxy-tert-butylsilyl)ethane,-   1,3-bis(diethoxy-tert-butylsilyl)propane,-   1,4-bis(diethoxy-tert-butylsilyl)butane,-   1,4-bis(diethoxy-tert-butylsilyl)benzene,-   bis(dipropoxy-tert-butylsilyl)methane,-   1,2-bis(dipropoxy-tert-butylsilyl)ethane,-   1,3-bis(dipropoxy-tert-butylsilyl)propane,-   1,4-bis(dipropoxy-tert-butylsilyl)butane,-   1,4-bis(dipropoxy-tert-butylsilyl)benzene,-   bis(diisopropoxy-tert-butylsilyl)methane,-   1,2-bis(diisopropoxy-tert-butylsilyl)ethane,-   1,3-bis(diisopropoxy-tert-butylsilyl)propane,-   1,4-bis(diisopropoxy-tert-butylsilyl)butane,-   1,4-bis(diisopropoxy-tert-butylsilyl)benzene,-   bis(dimethoxyphenylsilyl)methane,-   1,2-bis(dimethoxyphenylsilyl)ethane,-   1,3-bis(dimethoxyphenylsilyl)propane,-   1,4-bis(dimethoxyphenylsilyl)butane,-   1,4-bis(dimethoxyphenylsilyl)benzene,-   bis (diethoxyphenylsilyl) methane,-   1,2-bis(diethoxyphenylsilyl)ethane,-   1,3-bis(diethoxyphenylsilyl)propane,-   1,4-bis(diethoxyphenylsilyl)butane,-   1,4-bis(diethoxyphenylsilyl)benzene,-   bis(dipropoxyphenylsilyl)methane,-   1,2-bis(dipropoxyphenylsilyl)ethane,-   1,3-bis(dipropoxyphenylsilyl)propane,-   1,4-bis(dipropoxyphenylsilyl)butane,-   1,4-bis(dipropoxyphenylsilyl)benzene,-   bis(diisopropoxyphenylsilyl)methane,-   1,2-bis(diisopropoxyphenylsilyl)ethane,-   1,3-bis(diisopropoxyphenylsilyl)propane,-   1,4-bis(diisopropoxyphenylsilyl)butane,-   1,4-bis(diisopropoxyphenylsilyl)benzene,-   bis(dibutoxymethylsilyl)methane,-   1,2-bis(dibutoxymethylsilyl)ethane,-   1,3-bis(dibutoxymethylsilyl)propane,-   1,4-bis(dibutoxymethylsilyl)butane,-   1,4-bis(dibutoxymethylsilyl)benzene,-   bis(di-tert-butoxymethylsilyl)methane,-   1,2-bis(di-tert-butoxymethylsilyl)ethane,-   1,3-bis(di-tert-butoxymethylsilyl)propane,-   1,4-bis(di-tert-butoxymethylsilyl)butane,-   1,4-bis(di-tert-butoxymethylsilyl)benzene,-   bis(diacetoxymethylsilyl) methane,-   1,2-bis(diacetoxymethylsilyl)ethane,-   1,3-bis(diacetoxymethylsilyl)propane,-   1,4-bis(diacetoxymethylsilyl)butane,-   1,4-bis(diacetoxymethylsilyl)benzene,-   bis(diphenoxymethylsilyl) methane,-   1,2-bis(diphenoxymethylsilyl)ethane,-   1,3-bis(diphenoxymethylsilyl)propane,-   1,4-bis(diphenoxymethylsilyl)butane,-   1,4-bis(diphenoxymethylsilyl)benzene,-   bis(dibutoxyethylsilyl)methane,-   1,2-bis(dibutoxyethylsilyl)ethane,-   1,3-bis(dibutoxyethylsilyl)propane,-   1,4-bis(dibutoxyethylsilyl)butane,-   1,4-bis(dibutoxyethylsilyl)benzene,-   bis(di-tert-btoxyethylsilyl)methane,-   1,2-bis(di-tert-btoxyethylsilyl)ethane,-   1,3-bis(di-tert-btoxyethylsilyl)propane,-   1,4-bis(di-tert-btoxyethylsilyl)butane,-   1,4-bis(di-tert-btoxyethylsilyl)benzene,-   bis(diacetoxyethylsilyl)methane,-   1,2-bis(diacetoxyethylsilyl)ethane,-   1,3-bis(diacetoxyethylsilyl)propane,-   1,4-bis(diacetoxyethylsilyl)butane,-   1,4-bis(diacetoxyethylsilyl)benzene,-   bis(diphenoxyethylsilyl)methane,-   1,2-bis(diphenoxyethylsilyl)ethane,-   1,3-bis(diphenoxyethylsilyl)propane,-   1,4-bis(diphenoxyethylsilyl)butane,-   1,4-bis(diphenoxyethylsilyl)benzene,-   bis(dibutoxypropylsilyl) methane,-   1,2-bis(dibutoxypropylsilyl)ethane,-   1,3-bis(dibutoxypropylsilyl)propane,-   1,4-bis(dibutoxypropylsilyl)butane,-   1,4-bis(dibutoxypropylsilyl)benzene,-   bis(di-tert-butoxypropylsilyl) methane,-   1,2-bis(di-tert-butoxypropylsilyl)ethane,-   1,3-bis(di-tert-butoxypropylsilyl)propane,-   1,4-bis(di-tert-butoxypropylsilyl)butane,-   1,4-bis(di-tert-butoxypropylsilyl)benzene,-   bis(diacetoxypropylsilyl)methane,-   1,2-bis(diacetoxypropylsilyl)ethane,-   1,3-bis(diacetoxypropylsilyl)propane,-   1,4-bis(diacetoxypropylsilyl)butane,-   1,4-bis(diacetoxypropylsilyl)benzene,-   bis (diphenoxypropylsilyl) methane,-   1,2-bis(diphenoxypropylsilyl)ethane,-   1,3-bis(diphenoxypropylsilyl)propane,-   1,4-bis(diphenoxypropylsilyl)butane,-   1,4-bis(diphenoxypropylsilyl)benzene,-   bis(dibutoxyisopropylsilyl)methane,-   1,2-bis(dibutoxyisopropylsilyl)ethane,-   1,3-bis(dibutoxyisopropylsilyl)propane,-   1,4-bis(dibutoxyisopropylsilyl)butane,-   1,4-bis(dibutoxyisopropylsilyl)benzene,-   bis(di-tert-butoxyisopropylsilyl)methane,-   1,2-bis(di-tert-butoxyisopropylsilyl)ethane,-   1,3-bis(di-tert-butoxyisopropylsilyl)propane,-   1,4-bis(di-tert-butoxyisopropylsilyl)butane,-   1,4-bis(di-ter-tbutoxyisopropylsilyl)benzene,-   bis(diacetoxyisopropylsilyl) methane,-   1,2-bis(diacetoxyisopropylsilyl)ethane,-   1,3-bis(diacetoxyisopropylsilyl)propane,-   1,4-bis(diacetoxyisopropylsilyl)butane,-   1,4-bis(diacetoxyisopropylsilyl)benzene,-   bis(diphenoxyisopropylsilyl) methane,-   1,2-bis(diphenoxyisopropylsilyl)ethane,-   1,3-bis(diphenoxyisopropylsilyl)propane,-   1,4-bis(diphenoxyisopropylsilyl)butane,-   1,4-bis(diphenoxyisopropylsilyl)benzene,-   bis(dibutoxybutylsilyl) methane,-   1,2-bis(dibutoxybutylsilyl)ethane,-   1,3-bis(dibutoxybutylsilyl)propane,-   1,4-bis(dibutoxybutylsilyl)butane,-   1,4-bis(dibutoxybutylsilyl)benzene,-   bis(di-tert-butoxybutylsilyl)methane,-   1,2-bis(di-tert-butoxybutylsilyl)ethane,-   1,3-bis(di-tert-butoxybutylsilyl)propane,-   1,4-bis(di-tert-butoxybutylsilyl)butane,-   1,4-bis(di-tert-butoxybutylsilyl)benzene,-   bis(diacetoxybutylsilyl)methane,-   1,2-bis(diacetoxybutylsilyl)ethane,-   1,3-bis(diacetoxybutylsilyl)propane,-   1,4-bis(diacetoxybutylsilyl)butane,-   1,4-bis(diacetoxybutylsilyl)benzene,-   bis(diphoxybutylsilyl) methane,-   1,2-bis(diphoxybutylsilyl)ethane,-   1,3-bis(diphoxybutylsilyl)propane,-   1,4-bis(diphoxybutylsilyl)butane,-   1,4-bis(diphoxybutylsilyl)benzene,-   bis (dibutoxyphenylsilyl) methane,-   1,2-bis(dibutoxyphenylsilyl)ethane,-   1,3-bis(dibutoxyphenylsilyl)propane,-   1,4-bis(dibutoxyphenylsilyl)butane,-   1,4-bis(dibutoxyphenylsilyl)benzene,-   bis(di-tert-butoxyphenylsilyl) methane,-   1,2-bis(di-tert-butoxyphenylsilyl)ethane,-   1,3-bis(di-tert-butoxyphenylsilyl)propane,-   1,4-bis(di-tert-butoxyphenylsilyl)butane,-   1,4-bis(ditertbutoxyphenylsilyl)benzene,-   bis (diacetoxyphenylsilyl) methane,-   1,2-bis(diacetoxyphenylsilyl)ethane,-   1,3-bis(diacetoxyphenylsilyl)propane,-   1,4-bis(diacetoxyphenylsilyl)butane,-   1,4-bis(diacetoxyphenylsilyl)benzene,-   bis(diphenoxyphenylsilyl)methane,-   1,2-bis(diphenoxyphenylsilyl)ethane,-   1,3-bis(diphenoxyphenylsilyl)propane,-   1,4-bis(diphenoxyphenylsilyl)butane, and-   1,4-bis(diphenoxyphenylsilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (3) is notparticularly limited, and may be appropriately selected in accordancewith the objective. Specific examples thereof include:bis(dimethylmethoxysilyl)methane,

-   1,2-bis(dimethylmethoxysilyl)ethane,-   1,3-bis(dimethylmethoxysilyl)propane,-   1,4-bis(dimethylmethoxysilyl)butane,-   1,4-bis(dimethylmethoxysilyl)benzene,-   bis(dimethylethoxysilyl)methane,-   1,2-bis(dimethylethoxysilyl)ethane,-   1,3-bis(dimethylethoxysilyl)propane,-   1,4-bis(dimethylethoxysilyl)butane,-   1,4-bis(dimethylethoxysilyl)benzene,-   bis(dimethylpropoxysilyl)methane,-   1,2-bis(dimethylpropoxysilyl)ethane,-   1,3-bis(dimethylpropoxysilyl)propane,-   1,4-bis(dimethylpropoxysilyl)butane,-   1,4-bis(dimethylpropoxysilyl)benzene,-   bis(dimethylisopropoxysilyl)methane,-   1,2-bis(dimethylisopropoxysilyl)ethane,-   1,3-bis(dimethylisopropoxysilyl)propane,-   1,4-bis(dimethylisopropoxysilyl)butane,-   1,4-bis(dimethylisopropoxysilyl)benzene,-   bis(diethylmethoxysilyl) methane,-   1,2-bis(diethylmethoxysilyl)ethane,-   1,3-bis(diethylmethoxysilyl)propane,-   1,4-bis(diethylmethoxysilyl)butane,-   1,4-bis(diethylmethoxysilyl)benzene,-   bis(diethylethoxysilyl) methane,-   1,2-bis(diethylethoxysilyl)ethane,-   1,3-bis(diethylethoxysilyl)propane,-   1,4-bis(diethylethoxysilyl)butane,-   1,4-bis(diethylethoxysilyl)benzene,-   bis(diethylpropoxysilyl)methane,-   1,2-bis(diethylpropoxysilyl)ethane,-   1,3-bis(diethylpropoxysilyl)propane,-   1,4-bis(diethylpropoxysilyl)butane,-   1,4-bis(diethylpropoxysilyl)benzene,-   bis(diethylisopropoxysilyl)methane,-   1,2-bis(diethylisopropoxysilyl)ethane,-   1,3-bis(diethylisopropoxysilyl)propane,-   1,4-bis(diethylisopropoxysilyl)butane,-   1,4-bis(diethylisopropoxysilyl)benzene,-   bis(dipropylmethoxysilyl) methane,-   1,2-bis(dipropylmethoxysilyl)ethane,-   1,3-bis(dipropylmethoxysilyl)propane,-   1,4-bis(dipropylmethoxysilyl)butane,-   1,4-bis(dipropylmethoxysilyl)benzene,-   bis(dipropylethoxysilyl)methane,-   1,2-bis(dipropylethoxysilyl)ethane,-   1,3-bis(dipropylethoxysilyl)propane,-   1,4-bis(dipropylethoxysilyl)butane,-   1,4-bis(dipropylethoxysilyl)benzene,-   bis (dipropylpropoxysilyl) methane,-   1,2-bis(dipropylpropoxysilyl)ethane,-   1,3-bis(dipropylpropoxysilyl)propane,-   1,4-bis(dipropylpropoxysilyl)butane,-   1,4-bis(dipropylpropoxysilyl)benzene,-   bis (dipropylisopropoxysilyl) methane,-   1,2-bis(dipropylisopropoxysilyl)ethane,-   1,3-bis(dipropylisopropoxysilyl)propane,-   1,4-bis(dipropylisopropoxysilyl)butane,-   1,4-bis(dipropylisopropoxysilyl)benzene,-   bis(diisopropylmethoxysilyl)methane,-   1,2-bis(diisopropylmethoxysilyl)ethane,-   1,3-bis(diisopropylmethoxysilyl)propane,-   1,4-bis(diisopropylmethoxysilyl)butane,-   1,4-bis(diisopropylmethoxysilyl)benzene,-   bis(diisopropylethoxysilyl)methane,-   1,2-bis(diisopropylethoxysilyl)ethane,-   1,3-bis(diisopropylethoxysilyl)propane,-   1,4-bis(diisopropylethoxysilyl)butane,-   1,4-bis(diisopropylethoxysilyl)benzene,-   bis(diisopropylpropoxysilyl)methane,-   1,2-bis(diisopropylpropoxysilyl)ethane,-   1,3-bis(diisopropylpropoxysilyl)propane,-   1,4-bis(diisopropylpropoxysilyl)butane,-   1,4-bis(diisopropylpropoxysilyl)benzene,-   bis(diisopropylisopropoxysilyl)methane,-   1,2-bis(diisopropylisopropoxysilyl)ethane,-   1,3-bis(diisopropylisopropoxysilyl)propane,-   1,4-bis(diisopropylisopropoxysilyl)butane,-   1,4-bis(diisopropylisopropoxysilyl)benzene,-   bis(dibutylmethoxysilyl)methane,-   1,2-bis(dibutylmethoxysilyl)ethane,-   1,3-bis(dibutylmethoxysilyl)propane,-   1,4-bis(dibutylmethoxysilyl)butane,-   1,4-bis(dibutylmethoxysilyl)benzene,-   bis(dibutylethoxysilyl)methane,-   1,2-bis(dibutylethoxysilyl)ethane,-   1,3-bis(dibutylethoxysilyl)propane,-   1,4-bis(dibutylethoxysilyl)butane,-   1,4-bis(dibutylethoxysilyl)benzene,-   biutyls (dibutylpropoxysilyl) methane,-   1,2-bis(dibutylpropoxysilyl)ethane,-   1,3-bis(dibutylpropoxysilyl)propane,-   1,4-bis(dibutylpropoxysilyl)butane,-   1,4-bis(dibutylpropoxysilyl)benzene,-   bis (dibutylisopropoxysilyl) methane,-   1,2-bis(dibutylisopropoxysilyl)ethane,-   1,3-bis(dibutylisopropoxysilyl)propane,-   1,4-bis(dibutylisopropoxysilyl)butane,-   1,4-bis(dibutylisopropoxysilyl)benzene,-   bis(di-tert-butylmethoxysilyl)methane,-   1,2-bis(di-tert-butylmethoxysilyl)ethane,-   1,3-bis(di-tert-butylmethoxysilyl)propane,-   1,4-bis(di-tert-butylmethoxysilyl)butane,-   1,4-bis(di-tert-butylmethoxysilyl)benzene,-   bis(di-tert-butylethoxysilyl)methane,-   1,2-bis(di-tert-butylethoxysilyl)ethane,-   1,3-bis(di-tert-butylethoxysilyl)propane,-   1,4-bis(di-tert-butylethoxysilyl)butane,-   1,4-bis(di-tert-butylethoxysilyl)benzene,-   bis(di-tert-butylpropoxysilyl)methane,-   1,2-bis(di-tert-butylpropoxysilyl)ethane,-   1,3-bis(di-tert-butylpropoxysilyl)propane,-   1,4-bis(di-tert-butylpropoxysilyl)butane,-   1,4-bis(di-tert-butylpropoxysilyl)benzene,-   bis(di-tert-butylisopropoxysilyl)methane,-   1,2-bis(di-tert-butylisopropoxysilyl)ethane,-   1,3-bis(di-tert-butylisopropoxysilyl)propane,-   1,4-bis(di-tert-butylisopropoxysilyl)butane,-   1,4-bis(di-tert-butylisopropoxysilyl)benzene,-   bis(diphenylmethoxysilyl)methane,-   1,2-bis(diphenylmethoxysilyl)ethane,-   1,3-bis(diphenylmethoxysilyl)propane,-   1,4-bis(diphenylmethoxysilyl)butane,-   1,4-bis(diphenylmethoxysilyl)benzene,-   bis(diphenylethoxysilyl)methane,-   is 1,2-bis(diphenylethoxysilyl)ethane,-   1,3-bis(diphenylethoxysilyl)propane,-   1,4-bis(diphenylethoxysilyl)butane,-   1,4-bis(diphenylethoxysilyl)benzene,-   bis(diphenylpropoxysilyl)methane,-   1,2-bis(diphenylpropoxysilyl)ethane,-   1,3-bis(diphenylpropoxysilyl)propane,-   1,4-bis(diphenylpropoxysilyl)butane,-   1,4-bis(diphenylpropoxysilyl)benzene,-   bis(diphenylisopropoxysilyl) methane,-   1,2-bis(diphenylisopropoxysilyl)ethane,-   1,3-bis(diphenylisopropoxysilyl)propane,-   1,4-bis(diphenylisopropoxysilyl)butane,-   1,4-bis(diphenylisopropoxysilyl)benzene,-   bis(dimethylbutoxysilyl)methane,-   1,2-bis(dimethylbutoxysilyl)ethane,-   1,3-bis(dimethylbutoxysilyl)propane,-   1,4-bis(dimethylbutoxysilyl)butane,-   1,4-bis(dimethylbutoxysilyl)benzene,-   bis(dimethyl-tert-butoxysilyl) methane,-   1,2-bis(dimethyl-tert-butoxysilyl)ethane,-   1,3-bis(dimethyl-tert-butoxysilyl)propane,-   1,4-bis(dimethyl-tert-butoxysilyl)butane,-   1,4-bis(dimethyl-tert-butoxysilyl)benzene,-   bis (dimethylacetoxysilyl) methane,-   1,2-bis(dimethylacetoxysilyl)ethane,-   1,3-bis(dimethylacetoxysilyl)propane,-   1,4-bis(dimethylacetoxysilyl)butane,-   1,4-bis(dimethylacetoxysilyl)benzene,-   bis(dimethylphenoxysilyl)methane,-   1,2-bis(dimethylphenoxysilyl)ethane,-   1,3-bis(dimethylphenoxysilyl)propane,-   1,4-bis(dimethylphenoxysilyl)butane,-   1,4-bis(dimethylphenoxysilyl)benzene,-   bis (diethylbutoxysilyl) methane,-   1,2-bis(diethylbutoxysilyl)ethane,-   1,3-bis(diethylbutoxysilyl)propane,-   1,4-bis(diethylbutoxysilyl)butane,-   1,4-bis(diethylbutoxysilyl)benzene,-   bis(diethyl-tert-butoxysilyl)methane,-   1,2-bis(diethyl-tert-butoxysilyl)ethane,-   1,3-bis(diethyl-tert-butoxysilyl)propane,-   1,4-bis(diethyl-tert-butoxysilyl)butane,-   1,4-bis(diethyl-tert-butoxysilyl)benzene,-   bis(diethylacetoxysilyl)methane,-   1,2-bis(diethylacetoxysilyl)ethane,-   1,3-bis(diethylacetoxysilyl)propane,-   1,4-bis(diethylacetoxysilyl)butane,-   1,4-bis(diethylacetoxysilyl)benzene,-   bis(diethylphenoxysilyl) methane,-   1,2-bis(diethylphenoxysilyl)ethane,-   1,3-bis(diethylphenoxysilyl)propane,-   1,4-bis(diethylphenoxysilyl)butane,-   1,4-bis(diethylphenoxysilyl)benzene,-   bis(dipropylbutoxysilyl)methane,-   1,2-bis(dipropylbutoxysilyl)ethane,-   1,3-bis(dipropylbutoxysilyl)propane,-   1,4-bis(dipropylbutoxysilyl)butane,-   1,4-bis(dipropylbutoxysilyl)benzene,-   bis(dipropyl-tert-butoxysilyl)methane,-   1,2-bis(dipropyltertbutoxysilyl)ethane,-   1,3-bis(dipropyltertbutoxysilyl)propane,-   1,4-bis(dipropyltertbutoxysilyl)butane,-   1,4-bis(dipropyltertbutoxysilyl)benzene,-   bis(dipropylacetoxysilyl)methane,-   1,2-bis(dipropylacetoxysilyl)ethane,-   1,3-bis(dipropylacetoxysilyl)propane,-   1,4-bis(dipropylacetoxysilyl)butane,-   1,4-bis(dipropylacetoxysilyl)benzene,-   bis(dipropylphenoxysilyl) methane,-   1,2-bis(dipropylphenoxysilyl)ethane,-   1,3-bis(dipropylphenoxysilyl)propane,-   1,4-bis(dipropylphenoxysilyl)butane,-   1,4-bis(dipropylphenoxysilyl)benzene,-   bis(diisopropylbutoxysilyl) methane,-   1,2-bis(diisopropylbutoxysilyl)ethane,-   1,3-bis(diisopropylbutoxysilyl)propane,-   1,4-bis(diisopropylbutoxysilyl)butane,-   1,4-bis(diisopropylbutoxysilyl)benzene,-   bis (diisopropyl-tert-butoxysilyl)methane,-   1,2-bis(diisopropyltertbutoxysilyl)ethane,-   1,3-bis(diisopropyltertbutoxysilyl)propane,-   1,4-bis(diisopropyltertbutoxysilyl)butane,-   1,4-bis(diisopropyltertbutoxysilyl)benzene,-   bis(diisopropylacetoxysilyl) methane,-   1,2-bis(diisopropylacetoxysilyl)ethane,-   1,3-bis(diisopropylacetoxysilyl)propane,-   1,4-bis(diisopropylacetoxysilyl)butane,-   1,4-bis(diisopropylacetoxysilyl)benzene,-   bis(diisopropylphenoxysilyl)methane,-   1,2-bis(diisopropylphenoxysilyl)ethane,-   1,3-bis(diisopropylphenoxysilyl)propane,-   1,4-bis(diisopropylphenoxysilyl)butane,-   1,4-bis(diisopropylphenoxysilyl)benzene,-   bis(dibutylbutoxysilyl)methane,-   1,2-bis(dibutylbutoxysilyl)ethane,-   1,3-bis(dibutylbutoxysilyl)propane,-   1,4-bis(dibutylbutoxysilyl)butane,-   1,4-bis(dibutylbutoxysilyl)benzene,-   bis (dibutyl-tert-butoxysilyl) methane,-   1,2-bis(dibutyl-tert-butoxysilyl)ethane,-   1,3-bis(dibutyl-tert-butoxysilyl)propane,-   1,4-bis(dibutyl-tert-butoxysilyl)butane,-   1,4-bis(dibutyl-tert-butoxysilyl)benzene,-   bis(dibutylacetoxysilyl)methane,-   1,2-bis(dibutylacetoxysilyl)ethane,-   1,3-bis(dibutylacetoxysilyl)propane,-   1,4-bis(dibutylacetoxysilyl)butane,-   1,4-bis(dibutylacetoxysilyl)benzene,-   bis(dibutylphenoxysilyl)methane,-   1,2-bis(dibutylphenoxysilyl)ethane,-   1,3-bis(dibutylphenoxysilyl)propane,-   1,4-bis(dibutylphenoxysilyl)butane,-   1,4-bis(dibutylphenoxysilyl)benzene,-   bis(di-tert-butylbutoxysilyl)methane,-   1,2-bis(di-tert-butylbutoxysilyl)ethane,-   1,3-bis(di-tert-butylbutoxysilyl)propane,-   1,4-bis(di-tert-butylbutoxysilyl)butane,-   1,4-bis(di-tert-butylbutoxysilyl)benzene,-   bis(di-tert-butyl-tert-butoxysilyl)methane,-   1,2-bis(di-tert-butyl-tert-butoxysilyl)ethane,-   1,3-bis(di-tert-butyl-tert-butoxysilyl)propane,-   1,4-bis(di-tert-butyl-tert-butoxysilyl)butane,-   1,4-bis(di-tert-butyl-tert-butoxysilyl)benzene,-   bis(di-tert-butylacetoxysilyl) methane,-   1,2-bis(di-tert-butylacetoxysilyl)ethane,-   1,3-bis(di-tert-butylacetoxysilyl)propane,-   1,4-bis(di-tert-butylacetoxysilyl)butane,-   1,4-bis(di-tert-butylacetoxysilyl)benzene,-   bis(di-tert-butylphenoxysilyl)methane,-   1,2-bis(di-tert-butylphenoxysilyl)ethane,-   1,3-bis(di-tert-butylphenoxysilyl)propane,-   1,4-bis(di-tert-butylphenoxysilyl)butane,-   1,4-bis(di-tert-butylphenoxysilyl)benzene,-   bis(dibutoxy-tert-butylsilyl) methane,-   1,2-bis(dibutoxy-tert-butylsilyl)ethane,-   1,3-bis(dibutoxy-tert-butylsilyl)propane,-   1,4-bis(dibutoxy-tert-butylsilyl)butane,-   1,4-bis(dibutoxy-tert-butylsilyl)benzene,-   bis(di-tert-butoxy-tert-butylsilyl)methane,-   1,2-bis(di-tert-butoxy-tert-butylsilyl)ethane,-   1,3-bis(di-tert-butoxy-tert-butylsilyl)propane,-   1,4-bis(di-tert-butoxy-tert-butylsilyl)butane,-   1,4-bis(di-tert-butoxy-tert-butylsilyl)benzene,-   bis(diacetoxy-tert-butylsilyl)methane,-   1,2-bis(diacetoxy-tert-butylsilyl)ethane,-   1,3-bis(diacetoxy-tert-butylsilyl)propane,-   1,4-bis(diacetoxy-tert-butylsilyl)butane,-   1,4-bis(diacetoxy-tert-butylsilyl)benzene,-   bis(diphenoxy-tert-butylsilyl)methane,-   1,2-bis(diphenoxy-tert-butylsilyl)ethane,-   1,3-bis(diphenoxy-tert-butylsilyl)propane,-   1,4-bis(diphenoxy-tert-butylsilyl)butane,-   1,4-bis(diphenoxy-tert-butylsilyl)benzene,-   bis(diphenylbutoxysilyl)methane,-   1,2-bis(diphenylbutoxysilyl)ethane,-   1,3-bis(diphenylbutoxysilyl)propane,-   1,4-bis(diphenylbutoxysilyl)butane,-   1,4-bis(diphenylbutoxysilyl)benzene,-   bis(diphenyl-tert-butoxysilyl)methane,-   1,2-bis(diphenyl-tert-butoxysilyl)ethane,-   1,3-bis(diphenyl-tert-butoxysilyl)propane,-   1,4-bis(diphenyl-tert-butoxysilyl)butane,-   1,4-bis(diphenyl-tert-butoxysilyl)benzene,-   bis(diphenylacetoxysilyl)methane,-   1,2-bis(diphenylacetoxysilyl)ethane,-   1,3-bis(diphenylacetoxysilyl)propane,-   1,4-bis(diphenylacetoxysilyl)butane,-   1,4-bis(diphenylacetoxysilyl)benzene,-   bis (diphenylphenoxysilyl) methane,-   1,2-bis(diphenylphenoxysilyl)ethane,-   1,3-bis(diphenylphenoxysilyl)propane,-   1,4-bis(diphenylphenoxysilyl)butane, and-   1,4-bis(diphenylphenoxysilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (4) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane,tetrabutoxysilane, tetra-tert-butoxysilane, tetraacetoxysilane, andtetraphenoxysilane. These compounds may be used alone or in combinationof 2 or more.

The silicon compound expressed in the structural formula (5) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof includemethyltrimethoxysilane, ethyltrimethoxysilane, Propyltrimethoxysilane,isopropyltrimethoxysilane, butyltrimethoxysilane,tert-butyl-trimethoxysilane, phenyltrimethoxysilane,phenylmethyldimethoxysilane, Trimethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane,butyltriethoxysilane, tert-butyl-triethoxysilane, phenyltriethoxysilane,triethoxysilane, methyltripropoxysilane, ethyltripropoxysilane,propyltripropoxysilane, isopropyltripropoxysilane,butyltripropoxysilane, tert-butyl-tripropoxysilane,phenyltripropoxysilane, tripropoxysilane, methyltriisopropoxysilane,ethyltriisopropoxysilane, propyltriisopropoxysilane,isopropyltriisopropoxysilane, tert-butyl-triisopropoxysilane,phenyltriisopropoxysilane, triisopropoxysilane, methyltributoxysilane,ethyltributoxysilane, propyltributoxysilane, isopropyltributoxysilane,butyltributoxysilane, tert-butyl-tributoxysilane, phenyltributoxysilane,tributoxysilane, ethyl(tri-tert-butoxysilane),propyl(tri-tert-butoxysilane), isopropyl(tri-tert-butoxysilane),butyl(tri-tert-butoxysilane), tert-butyl-tri-tert-butoxysilane,phenyl(tri-tert-butoxysilane), phenylmethyl(di-tert-butoxysilane),tri-tert-butoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane,propyltriacetoxysilane, isopropyltriacetoxysilane,butyltriacetoxysilane, tert-butyl-triacetoxysilane,phenyltriacetoxysilane, triacetoxysilane, methyltriphenoxysilane,ethyltriphenoxysilane, propyltriphenoxysilane,isopropyltriphenoxysilane, butyltriphenoxysilane,tert-butyl-triphenoxysilane, phenyltriphenoxysilane,phenylpropyldiphenoxysilane, and triphenoxysilane. These compounds maybe used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (6) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof includedimethyldimethoxysilane, diethyldimethoxysilane,dipropyldimethoxysilane, diisopropyldimethoxysilane,dibutyldimethoxysilane, di-tert-butyl-dimethoxysilane,diphenyldimethoxysilane, dimethylphenylmethoxysilane,phenylethyldimethoxysilane, phenylpropyldimethoxysilane,phenylisopropyldimethoxysilane, phenylbutyldimethoxysilane,phenyl(tert-butyl)dimethoxysilane, dimethoxysilane,methyldimethoxysilane, ethyldimethoxysilane, propyldimethoxysilane,isopropyldimethoxysilane, butyldimethoxysilane,tert-butyl-dimethoxysilane, diphenyldimethoxysilane,dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane,diisopropyldiethoxysilane, dibutyldiethoxysilane,di-tert-butyl-diethoxysilane, diphenyldiethoxysilane,phenylmethyldiethoxysilane, phenylethyldiethoxysilane,phenylpropyldiethoxysilane, phenylisopropyldiethoxysilane,phenylbutyldiethoxysilane, phenyl(tert-butyl)diethoxysilane,diethoxysilane, methyldiethoxysilane, ethyldiethoxysilane,propyldiethoxysilane, isopropyldiethoxysilane, butyldiethoxysilane,tert-butyl-diethoxysilane, diphenyldiethoxysilane,dimethyldipropoxysilane, diethyldipropoxysilane,dipropyldipropoxysilane, diisopropyldipropoxysilane,dibutyldipropoxysilane, di-tert-butyl-dipropoxysilane,diphenyldipropoxysilane, phenylmethyldipropoxysilane,phenylethyldipropoxysilane, phenylpropyldipropoxysilane,phenylisopropyldipropoxysilane, phenylbutyldipropoxysilane,phenyl(tert-butyl)dipropoxysilane, dipropoxysilane,methyldipropoxysilane, ethyldipropoxysilane, ethylpropoxysilane,propyldipropoxysilane, isopropyldipropoxysilane, butyldipropoxysilane,tert-butyl-dipropoxysilane, diphenyldipropoxysilane,dimethyldiisopropoxysilane, diethyldiisopropoxysilane,dipropyldiisopropoxysilane, diisopropyldiisopropoxysilane,dibutyldiisopropoxysilane, di-tert-butyl-diisopropoxysilane,diphenyldiisopropoxysilane, phenylmethyldiisopropoxysilane,phenylethyldiisopropoxysilane, phenylpropyldiisopropoxysilane,phenylisopropyldiisopropoxysilane, phenylbutyldiisopropoxysilane,phenyl(tert-butyl)diisopropoxysilane, diisopropoxysilane,methyldiisopropoxysilane, ethyldiisopropoxysilane,propyldiisopropoxysilane, isopropyldiisopropoxysilane,butyldiisopropoxysilane, tert-butyl-diisopropoxysilane,diphenyldiisopropoxysilane, dimethyldibutoxysilane,diethyldibutoxysilane, dipropyldibutoxysilane,diisopropyldibutoxysilane, dibutyldibutoxysilane,di-tert-butyl-dibutoxysilane, diphenyldibutoxysilane,phenylmethyldibutoxysilane, phenylethyldibutoxysilane,phenylpropyldibutoxysilane, phenylisopropyldibutoxysilane,phenylbutyldibutoxysilane, phenyl(tert-butyl)dibutoxysilane,dibutoxysilane, methyldibutoxysilane, ethyldibutoxysilane,propyldibutoxysilane, isopropyldibutoxysilane, butyldibutoxysilane,tert-butyl-dibutoxysilane, diphenyldibutoxysilane,diethyl(di-tert-butoxysilane), dipropyl(di-tert-butoxysilane),diisopropyl(di-tert-butoxysilane), dibutyl(di-tert-butoxysilane),di-tert-butyl-di-tert-butoxysilane, diphenyl(di-tert-butoxysilane),phenylethyl(di-tert-butoxysilane), phenylpropyl(di-tert-butoxysilane),phenylisopropyl(di-tert-butoxysilane),phenylbutyl(di-tert-butoxysilane),phenyl(tert-butyl)(di-tert-butoxysilane), di-tert-butoxysilane,methyl(di-tert-butoxysilane), ethyl(di-tert-butoxysilane),propyl(di-tert-butoxysilane), isopropyl(di-tert-butoxysilane),butyl(di-tert-butoxysilane), tert-butyl-di-tert-butoxysilane,diphenyl(di-tert-butoxysilane), dimethyldiacetoxysilane,diethyldiacetoxysilane, dipropyldiacetoxysilane,diisopropyldiacetoxysilane, di-tert-butyl-diacetoxysilane,diphenyldiacetoxysilane, phenylmethyldiacetoxysilane,phenylethyldiacetoxysilane, phenylpropyldiacetoxysilane,phenylisopropyldiacetoxysilane, phenylbutyldiacetoxysilane,phenyl(tert-butyl)diacetoxysilane, diacetoxysilane,methyldiacetoxysilane, ethyldiacetoxysilane, propyldiacetoxysilane,isopropyldiacetoxysilane, butyldiacetoxysilane,tert-butyl-diacetoxysilane, diphenyldiacetoxysilane,dimethyldiphenoxysilane, diethyldiphenoxysilane,dipropyldiphenoxysilane, diisopropyldiphenoxysilane,dibutyldiphenoxysilane, di-tert-butyl-diphenoxysilane,diphenyldiphenoxysilane, phenylmethyldiphenoxysilane,phenylethyldiphenoxysilane, phenylisopropyldiphenoxysilane,phenylbutyldiphenoxysilane, phenyl-tert-butyl-diphenoxysilane,diphenoxysilane, methyldiphenoxysilane, ethyldiphenoxysilane,propyldiphenoxysilane, isopropyldiphenoxysilane, butyldiphenoxysilane,tert-butyl-diphenoxysilane, and diphenyldiphenoxysilane. These compoundsmay be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (7) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof includetrimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane,triisopropylmethoxysilane, tributylmethoxysilane,tri-tert-butylmethoxysilane, triphenylmethoxysilane,diphenylmethylmethoxysilane, diethylphenylmethoxysilane,diphenylethylmethoxysilane, dipropylphenylmethoxysilane,diphenylpropylmethoxysilane, diisopropylphenylmethoxysilane,diphenylisopropylmethoxysilane, dibutylphenylmethoxysilane,dibutylmethylmethoxysilane, di-tert-butylphenylmethoxysilane,diphenyl-tert-butylmethoxysilane, monomethoxysilane,methylmethoxysilane, ethylmethoxysilane, propylmethoxysilane,isopropylmethoxysilane, butylmethoxysilane, tert-butylmethoxysilane,phenylmethoxysilane, methylphenylmethoxysilane, ethylphenylethoxysilane,propylphenylethoxysilane, isopropylphenylmethoxysilane,butylphenylmethoxysilane, tert-butylphenylmethoxysilane,trimethylethoxysilane, triethylethoxysilane, tripropylethoxysilane,triisopropylethoxysilane, tributylethoxysilane,tri-tert-butylethoxysilane, triphenylethoxysilane,dimethylphenylethoxysilane, diphenylmethylethoxysilane,diethylphenylethoxysilane, diphenylethylethoxysilane,dipropylphenylethoxysilane, diphenylpropylethoxysilane,diisopropylphenylethoxysilane, diphenylisopropylethoxysilane,dibutylphenylethoxysilane, dibutylmethylethoxysilane,di-tert-butylphenylethoxysilane, diphenyl-tert-butylethoxysilane,monoethoxysilane, methylethoxysilane, ethylethoxysilane,propylethoxysilane, isopropylethoxysilane, butylethoxysilane,tert-butylethoxysilane, phenylethoxysilane, methylphenylethoxysilane,ethylphenylethoxysilane, propylphenylethoxysilane,isopropylphenylethoxysilane, butylphenylethoxysilane,tert-butylphenylethoxysilane, trimethylpropoxysilane,triethylpropoxysilane, tripropylpropoxysilane,triisopropylpropoxysilane, tributylpropoxysilane,tri-tert-butylpropoxysilane, triphenylpropoxysilane,dimethylphenylpropoxysilane, diphenylmethylpropoxysilane,diethylphenylpropoxysilane, diphenylethylpropoxysilane,dipropylphenylpropoxysilane, diphenylpropylpropoxysilane,diisopropylphenylpropoxysilane, diphenylisopropylpropoxysilane,dibutylphenylpropoxysilane, dibutylmethylpropoxysilane,di-tert-butylphenylpropoxysilane, diphenyl-tert-butylpropoxysilane,monopropoxysilane, methylpropoxysilane, propylpropoxysilane,isopropylpropoxysilane, butylpropoxysilane, tert-butylpropoxysilane,phenylpropoxysilane, methylphenylpropoxysilane,ethylphenylpropoxysilane, propylphenylethoxysilane,isopropylphenylpropoxysilane, butylphenylpropoxysilane,tert-butylphenylpropoxysilane, trimethylisopropoxysilane,triethylisopropoxysilane, tripropylisopropoxysilane,triisopropylisopropoxysilane, butyltriisopropoxysilane,tributylisopropoxysilane, tri-tert-butylisopropoxysilane,triphenylisopropoxysilane, dimethylphenylisopropoxysilane,diphenylmethylisopropoxysilane, diethylphenylisopropoxysilane,diphenylethylisopropoxysilane, dipropylphenylisopropoxysilane,diphenylpropylisopropoxysilane, diisopropylphenylisopropoxysilane,diphenylisopropylisopropoxysilane, dibutylphenylisopropoxysilane,dibutylmethylisopropoxysilane, di-tert-butylphenylisopropoxysilane,diphenyl-tert-butylisopropoxysilane, monoisopropoxysilane,methylisopropoxysilane, ethylisopropoxysilane, propylisopropoxysilane,isopropylisopropoxysilane, butylisopropoxysilane,tert-butylisopropoxysilane, phenylisopropoxysilane,methylphenylisopropoxysilane, ethylphenylisopropoxysilane,propylphenylethoxysilane, isopropylphenylisopropoxysilane,butylphenylisopropoxysilane, tert-butylphenylisopropoxysilane,trimethylbutoxysilane, triethylbutoxysilane, tripropylbutoxysilane,triisopropylbutoxysilane, tributylbutoxysilane,tri-tert-butylbutoxysilane, triphenylbutoxysilane,dimethylphenylbutoxysilane, diphenylmethylbutoxysilane,diethylphenylbutoxysilane, diphenylethylbutoxysilane,dipropylphenylbutoxysilane, diphenylpropylbutoxysilane,diisopropylphenylbutoxysilane, diphenylisopropylbutoxysilane,dibutylphenylbutoxysilane, dibutylmethylbutoxysilane,di-tert-butylphenylbutoxysilane, diphenyl-tert-butylbutoxysilane,monobutoxysilane, methylbutoxysilane, ethylbutoxysilane,propylbutoxysilane, isopropylbutoxysilane, butylbutoxysilane,tert-butylbutoxysilane, phenylbutoxysilane, methylphenylbutoxysilane,ethylphenylbutoxysilane, propylphenylethoxysilane,isopropylphenylbutoxysilane, butylphenylbutoxysilane,tert-butylphenylbutoxysilane, methyl-tri-tert-butoxysilane,dimethyl-di-tert-butoxysilane, trimethyl-tert-butoxysilane,triethyl-tert-butoxysilane, tripropyl-tert-butoxysilane,triisopropyl-tert-butoxysilane, tributyl-tert-butoxysilane,tri-tert-butyl-tert-butoxysilane, triphenyl-tert-butoxysilane,dimethylphenyl-tert-butoxysilane, diphenylmethyl-tert-butoxysilane,diethylphenyl-tert-butoxysilane, diphenylethyl-tert-butoxysilane,dipropylphenyl-tert-butoxysilane, diphenylpropyl-tert-butoxysilane,diisopropylphenyl-tert-butoxysilane,diphenylisopropyl-tert-butoxysilane, dibutylphenyl-tert-butoxysilane,dibutylmethyl-tert-butoxysilane, di-tert-butylphenyltertbutoxysilane,diphenyl-tert-butyl-tert-butoxysilane, mono-tert-butoxysilane,methyl-tert-butoxysilane, ethyl-tert-butoxysilane,propyl-tert-butoxysilane, isopropyl-tert-butoxysilane,butyl-tert-butoxysilane, tert-butyl-tert-butoxysilane,phenyl-tert-butoxysilane, methylphenyl-tert-butoxysilane,ethylphenyl-tert-butoxysilane, ropylphenylethoxysilane,isopropylphenyl-tert-butoxysilane, butylphenyl-tert-butoxysilane,tert-butylphenyl-tert-butoxysilane, trimethylacetoxysilane,triethylacetoxysilane, tripropylacetoxysilane,triisopropylacetoxysilane, dibutyldiacetoxysilane,tributylacetoxysilane, tri-tert-butylacetoxysilane,triphenylacetoxysilane, dimethylphenylacetoxysilane,diphenylmethylacetoxysilane, diethylphenylacetoxysilane,diphenylethylacetoxysilane, dipropylphenylacetoxysilane,diphenylpropylacetoxysilane, diisopropylphenylacetoxysilane,diphenylisopropylacetoxysilane, dibutylphenylacetoxysilane,dibutylmethylacetoxysilane, di-tert-butylphenylacetoxysilane,diphenyl-tert-butylacetoxysilane, monoacetoxysilane,methylacetoxysilane, ethylacetoxysilane, propylacetoxysilane,isopropylacetoxysilane, butylacetoxysilane, tert-butylacetoxysilane,phenylacetoxysilane, methylphenylacetoxysilane,ethylphenylacetoxysilane, propylphenylethoxysilane,isopropylphenylacetoxysilane, butylphenylacetoxysilane,tert-butylphenylacetoxysilane, trimethylphenoxysilane,triethylphenoxysilane, tripropylphenoxysilane,triisopropylphenoxysilane, tributylphenoxysilane,tri-tert-butylphenoxysilane, triphenylphenoxysilane,dimethylphenylphenoxysilane, diphenylmethylphenoxysilane,diethylphenylphenoxysilane, diphenylethylphenoxysilane,dipropylphenylphenoxysilane, diphenylpropylphenoxysilane,diisopropylphenylphenoxysilane, diphenylisopropylphenoxysilane,dibutylphenylphenoxysilane, dibutylmethylphenoxysilane,di-tert-butylphenylphenoxysilane, diphenyl-tert-butylphenoxysilane,monophenoxysilane, methylphenoxysilane, ethylphenoxysilane,propylphenoxysilane, isopropylphenoxysilane, butylphenoxysilane,tert-butylphenoxysilane, phenylphenoxysilane, methylphenylphenoxysilane,ethylphenylphenoxysilane, propylphenylethoxysilane,isopropylphenylphenoxysilane, butylphenylphenoxysilane, andtert-butylphenylphenoxysilane. These compounds may be used alone or incombination of 2 or more.

In addition, when n=0 in the general formulas (1) to (7), thecombination of at least one of the silicon compounds expressed by thefollowing structural formulas (8) to (10), and at least one of thesilicon compounds expressed by the following structural formulas (11) to(14) may be suitably used.

Here, in the structural formulas (8) to (14), R¹ may be the same as ordifferent from each other, represents one selected from the groupconsisting of a chlorine atom, a bromine atom, a fluorine atom, and ahydrogen atom. R² represents one selected from the group consisting of ahydrocarbon with a carbon number of 1 to 4, an aromatic hydrocarbon, anda hydrogen atom. R³ may be the same as or different from each other, andrepresents one selected from the group consisting of a hydrocarbon witha carbon number of 1 to 3 and an aromatic hydrocarbon.

The silicon compound expressed by the structural formula (8) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include:

-   bis(trichlorosilyl)methane,-   1,2-bis(trichlorosilyl)ethane,-   1,3-bis(trichlorosilyl)propane,-   1,4-bis(trichlorosilyl)butane,-   1,4-bis(trichlorosilyl)benzene,-   bis(trifluorosilyl)methane,-   1,2-bis(trifluorosilyl)ethane,-   1,3-bis(trifluorosilyl)propane,-   1,4-bis(trifluorosilyl)butane,-   1,4-bis(trifluorosilyl)benzene,-   bis (tribromosilyl) methane,-   1,2-bis(tribromosilyl)ethane,-   1,3-bis(tribromosilyl)propane,-   1,4-bis(tribromosilyl)butane,-   1,4-bis(tribromosilyl)benzene,-   bis (trihydrosilyl) methane,-   1,2-bis(trihydrosilyl)ethane,-   1,3-bis(trihydrosilyl)propane,-   1,4-bis(trihydrosilyl)butane,-   1,4-bis(trihydrosilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (9) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include:

-   bis(dichloromethylsilyl)methane,-   1,2-bis(dichloromethylsilyl)ethane,-   1,3-bis(dichloromethylsilyl)propane,-   1,4-bis(dichloromethylsilyl)butane,-   1,4-bis(dichloromethylsilyl)benzene,-   bis(difluoromethylsilyl)methane,-   1,2-bis(difluoromethylsilyl)ethane,-   1,3-bis(difluoromethylsilyl)propane,-   1,4-bis(difluoromethylsilyl)butane,-   1,4-bis(difluoromethylsilyl)benzene,-   bis (dibromomethylsilyl) methane,-   1,2-bis(dibromomethylsilyl)ethane,-   1,3-bis(dibromomethylsilyl)propane,-   1,4-bis(dibromomethylsilyl)butane,-   1,4-bis(dibromomethylsilyl)benzene,-   bis(dihydromethylsilyl) methane,-   1,2-bis(dihydromethylsilyl)ethane,-   1,3-bis(dihydromethylsilyl)propane,-   1,4-bis(dihydromethylsilyl)butane,-   1,4-bis(dihydromethylsilyl)benzene,-   bis(dichloroethylsilyl)methane,-   1,2-bis(dichloroethylsilyl)ethane,-   1,3-bis(dichloroethylsilyl)propane,-   1,4-bis(dichloroethylsilyl)butane,-   1,4-bis(dichloroethylsilyl)benzene,-   bis(difluoroethylsilyl)methane,-   1,2-bis(difluoroethylsilyl)ethane,-   1,3-bis(difluoroethylsilyl)propane,-   1,4-bis(difluoroethylsilyl)butane,-   1,4-bis(difluoroethylsilyl)benzene,-   bis (dibromoethylsilyl) methane,-   1,2-bis(dibromoethylsilyl)ethane,-   1,3-bis(dibromoethylsilyl)propane,-   1,4-bis(dibromoethylsilyl)butane,-   1,4-bis(dibromoethylsilyl)benzene,-   bis(dihydroethylsilyl)methane,-   1,2-bis(dihydroethylsilyl)ethane,-   1,3-bis(dihydroethylsilyl)propanem,-   1,4-bis(dihydroethylsilyl)butane,-   1,4-bis(dihydroethylsilyl)benzene,-   bis(dichloropropylsilyl)methane,-   1,2-bis(dichloropropylsilyl)ethane,-   1,3-bis(dichloropropylsilyl)propane,-   1,4-bis(dichloropropylsilyl)butane,-   1,4-bis(dichloropropylsilyl)benzene,-   bis(difluoropropylsilyl)methane,-   1,2-bis(difluoropropylsilyl)ethane,-   1,3-bis(difluoropropylsilyl)propane,-   1,4-bis(difluoropropylsilyl)butane,-   1,4-bis(difluoropropylsilyl)benzene,-   bis(dibromopropylsilyl)methane,-   1,2-bis(dibromopropylsilyl)ethane,-   1,3-bis(dibromopropylsilyl)propane,-   1,4-bis(dibromopropylsilyl)butane,-   1,4-bis(dibromopropylsilyl)benzene,-   bis(dihydropropylsilyl) methane,-   1,2-bis(dihydropropylsilyl)ethane,-   1,3-bis(dihydropropylsilyl)propane,-   1,4-bis(dihydropropylsilyl)butane,-   1,4-bis(dihydropropylsilyl)benzene,-   bis(dichloroisopropylsilyl) methane,-   1,2-bis(dichloroisopropylsilyl)ethane,-   1,3-bis(dichloroisopropylsilyl)propane,-   1,4-bis(dichloroisopropylsilyl)butane,-   1,4-bis(dichloroisopropylsilyl)benzene,-   bis(difluoroisopropylsilyl)methane,-   1,2-bis(difluoroisopropylsilyl)ethane,-   1,3-bis(difluoroisopropylsilyl)propane,-   1,4-bis(difluoroisopropylsilyl)butane,-   1,4-bis(difluoroisopropylsilyl)benzene,-   bis(dibromoisopropylsilyl)methane,-   1,2-bis(dibromoisopropylsilyl)ethane,-   1,3-bis(dibromoisopropylsilyl)propane,-   1,4-bis(dibromoisopropylsilyl)butane,-   1,4-bis(dibromoisopropylsilyl)benzene,-   bis(dihydroisopropylsilyl)methane,-   1,2-bis(dihydroisopropylsilyl)ethane,-   1,3-bis(dihydroisopropylsilyl)propane,-   1,4-bis(dihydroisopropylsilyl)butane,-   1,4-bis(dihydroisopropylsilyl)benzene,-   bis(dichlorobutylsilyl)methane,-   1,2-bis(dichlorobutylsilyl)ethane,-   1,3-bis(dichlorobutylsilyl)propane,-   1,4-bis(dichlorobutylsilyl)butane,-   1,4-bis(dichlorobutylsilyl)benzene,-   bis(difluorobutylsilyl)methane,-   1,2-bis(difluorobutylsilyl)ethane,-   1,3-bis(difluorobutylsilyl)propane,-   1,4-bis(difluorobutylsilyl)butane,-   1,4-bis(difluorobutylsilyl)benzene,-   bis(dibromobutylsilyl)methane,-   1,2-bis(dibromobutylsilyl)ethane,-   1,3-bis(dibromobutylsilyl)propane,-   1,4-bis(dibromobutylsilyl)butane,-   1,4-bis(dibromobutylsilyl)benzene,-   bis(dihydrobutylsilyl)methane,-   1,2-bis(dihydrobutylsilyl)ethane,-   1,3-bis(dihydrobutylsilyl)propane,-   1,4-bis(dihydrobutylsilyl)butane,-   1,4-bis(dihydrobutylsilyl)benzene,-   bis (dichloro-tert-butylsilyl) methane,-   1,2-bis(dichloro-tert-butylsilyl)ethane,-   1,3-bis(dichloro-tert-butylsilyl)propane,-   1,4-bis(dichloro-tert-butylsilyl)butane,-   1,4-bis(dichloro-tert-butylsilyl)benzene,-   bis(difluoro-tert-butylsilyl)methane,-   1,2-bis(difluoro-tert-butylsilyl)ethane,-   1,3-bis(difluoro-tert-butylsilyl)propane,-   1,4-bis(difluoro-tert-butylsilyl)butane,-   1,4-bis(difluoro-tert-butylsilyl)benzene,-   bis(dibromo-tert-butylsilyl) methane,-   1,2-bis(dibromo-tert-butylsilyl)ethane,-   1,3-bis(dibromo-tert-butylsilyl)propane,-   1,4-bis(dibromo-tert-butylsilyl)butane,-   1,4-bis(dibromo-tert-butylsilyl)benzene,-   bis(dihydro-tert-butylsilyl)methane,-   1,2-bis(dihydro-tert-butylsilyl)ethane,-   1,3-bis(dihydro-tert-butylsilyl)propane,-   1,4-bis(dihydro-tert-butylsilyl)butane,-   1,4-bis(dihydro-tert-butylsilyl)benzene,-   bis(dichlorophenylsilyl)methane,-   1,2-bis(dichlorophenylsilyl)ethane,-   1,3-bis(dichlorophenylsilyl)propane,-   1,4-bis(dichlorophenylsilyl)butane,-   1,4-bis(dichlorophenylsilyl)benzene,-   bis(difluorophenylsilyl)methane,-   1,2-bis(difluorophenylsilyl)ethane,-   1,3-bis(difluorophenylsilyl)propane,-   1,4-bis(difluorophenylsilyl)butane,-   1,4-bis(difluorophenylsilyl)benzene,-   bis(dibromophenylsilyl)methane,-   1,2-bis(dibromophenylsilyl)ethane,-   1,3-bis(dibromophenylsilyl)propane,-   1,4-bis(dibromophenylsilyl)butane,-   1,4-bis(dibromophenylsilyl)benzene,-   bis(dihydrophenylsilyl) methane,-   1,2-bis(dihydrophenylsilyl)ethane,-   1,3-bis(dihydrophenylsilyl)propane,-   1,4-bis(dihydrophenylsilyl)butane, and-   1,4-bis(dihydrophenylsilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (10) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include:

-   bis(dimethylchlorosilyl)methane,-   1,2-bis(dimethylchlorosilyl)ethane,-   1,3-bis(dimethylchlorosilyl)propane,-   1,4-bis(dimethylchlorosilyl)butane,-   1,4-bis(dimethylchlorosilyl)benzene,-   bis(dimethylfluorosilyl)methane,-   1,2-bis(dimethylfluorosilyl)ethane,-   1,3-bis(dimethylfluorosilyl) propane,-   1,4-bis(dimethylfluorosilyl)butane,-   1,4-bis(dimethylfluorosilyl)benzene,-   bis(dimethylbromosilyl)methane,-   1,2-bis(dimethylbromosilyl)ethane,-   1,3-bis(dimethylbromosilyl)propane,-   1,4-bis(dimethylbromosilyl)butane,-   1,4-bis(dimethylbromosilyl)benzene,-   bis (dimethylhydrosilyl) methane,-   1,2-bis(dimethylhydrosilyl)ethane,-   1,3-bis(dimethylhydrosilyl)propane,-   1,4-bis(dimethylhydrosilyl)butane,-   1,4-bis(dimethylhydrosilyl)benzene,-   bis(diethylchlorosilyl)methane,-   1,2-bis(diethylchlorosilyl)ethane,-   1,3-bis(diethylchlorosilyl)propane,-   1,4-bis(diethylchlorosilyl)butane,-   1,4-bis(diethylchlorosilyl)benzene,-   bis (diethyffluorosilyl) methane,-   1,2-bis(diethylfluorosilyl)ethane,-   1,3-bis(diethylfluorosilyl)propane,-   1,4-bis(diethylfluorosilyl)butane,-   1,4-bis(diethylfluorosilyl)benzene,-   bis (diethylbromosilyl) methane,-   1,2-bis(diethylbromosilyl)ethane,-   1,3-bis(diethylbromosilyl)propane,-   1,4-bis(diethylbromosilyl)butane,-   1,4-bis(diethylbromosilyl)benzene,-   bis(diethylhydrosilyl)methane,-   1,2-bis(diethylhydrosilyl)ethane,-   1,3-bis(diethylhydrosilyl)propane,-   1,4-bis(diethylhydrosilyl)butane,-   1,4-bis(diethylhydrosilyl)benzene,-   bis(dipropylchlorosilyl)methane,-   1,2-bis(dipropylchlorosilyl)ethane,-   1,3-bis(dipropylchlorosilyl)propane,-   1,4-bis(dipropylchlorosilyl)butane,-   1,4-bis(dipropylchlorosilyl)benzene,-   bis(dipropylfluorosilyl)methane,-   1,2-bis(dipropylfluorosilyl)ethane,-   1,3-bis(dipropylfluorosilyl)propane,-   1,4-bis(dipropyffluorosilyl)butane,-   1,4-bis(dipropyfluorosilyl)benzene,-   bis(dipropylbromosilyl) methane,-   1,2-bis(dipropylbromosilyl)ethane,-   1,3-bis(dipropylbromosilyl)propane,-   1,4-bis(dipropylbromosilyl)butane,-   1,4-bis(dipropylbromosilyl)benzene,-   bis (dipropylhydrosilyl) methane,-   1,2-bis(dipropylhydrosilyl)ethane,-   1,3-bis(dipropylhydrosilyl)propane,-   1,4-bis(dipropylhydrosilyl)butane,-   1,4-bis(dipropylhydrosilyl)benzene,-   bis(diisopropylchlorosilyl) methane,-   1,2-bis(diisopropylchlorosilyl)ethane,-   1,3-bis(diisopropylchlorosilyl)propane,-   1,4-bis(diisopropylchlorosilyl)butane,-   1,4-bis(diisopropylchlorosilyl)benzene,-   bis(diisopropylfluorosilyl)methane,-   1,2-bis(diisopropylfluorosilyl)ethane,-   1,3-bis(diisopropylfluorosilyl)propane,-   1,4-bis(diisopropylfluorosilyl)butane,-   1,4-bis(diisopropylfluorosilyl)benzene,-   bis(diisopropylbromosilyl) methane,-   1,2-bis(diisopropylbromosilyl)ethane,-   1,3-bis(diisopropylbromosilyl)propane,-   1,4-bis(diisopropylbromosilyl)butane,-   1,4-bis(diisopropylbromosilyl)benzene,-   bis (diisopropylhydrosilyl)methane,-   1,2-bis(diisopropylhydrosilyl)ethane,-   1,3-bis(diisopropylhydrosilyl)propane,-   1,4-bis(diisopropylhydrosilyl)butane,-   1,4-bis(diisopropylhydrosilyl)benzene,-   bis(dibutylchlorosilyl)methane,-   1,2-bis(dibutylchlorosilyl)ethane,-   1,3-bis(dibutylchlorosilyl)propane,-   1,4-bis(dibutylchlorosilyl)butane,-   1,4-bis(dibutylchlorosilyl)benzene,-   bis(dibutylfluorosilyl)methane,-   1,2-bis(dibutylfluorosilyl)ethane,-   1,3-bis(dibutylfluorosilyl)propane,-   1,4-bis(dibutylfluorosilyl)butane,-   1,4-bis(dibutylfluorosilyl)benzene,-   bis(dibutylbromosilyl)methane,-   1,2-bis(dibutylbromosilyl)ethane,-   1,3-bis(dibutylbromosilyl)propane,-   1,4-bis(dibutylbromosilyl)butane,-   1,4-bis(dibutylbromosilyl)benzene,-   bis(dibutylhydrosilyl) methane,-   1,2-bis(dibutylhydrosilyl)ethane,-   1,3-bis(dibutylhydrosilyl)propane,-   1,4-bis(dibutylhydrosilyl)butane,-   1,4-bis(dibutylhydrosilyl)benzene,-   bis(di-tert-butylchlorosilyl) methane,-   1,2-bis(di-tert-butylchlorosilyl)ethane,-   1,3-bis(di-tert-butylchlorosilyl)propane,-   1,4-bis(di-tert-butylchlorosilyl)butane,-   1,4-bis(di-tert-butylchlorosilyl)benzene,-   bis(di-tert-butylfluorosilyl)methane,-   1,2-bis(di-tert-butylfluorosilyl)ethane,-   1,3-bis(di-tert-butyfluorosilyl)propane,-   1,4-bis(di-tert-butylfluorosilyl)butane,-   1,4-bis(di-tert-butylfluorosilyl)benzene,-   bis(di-tert-butylbromosilyl) methane,-   1,2-bis(di-tert-butylbromosilyl)ethane,-   1,3-bis(di-tert-butylbromosilyl)propane,-   1,4-bis(di-tert-butylbromosilyl)butane,-   1,4-bis(di-tert-butylbromosilyl)benzene,-   bis(di-tert-butylhydrosilyl) methane,-   1,2-bis(di-tert-butylhydrosilyl)ethane,-   1,3-bis(di-tert-butylhydrosilyl)propane,-   1,4-bis(di-tert-butylhydrosilyl)butane,-   1,4-bis(di-tert-butylhydrosilyl)benzene,-   bis(diphenylchlorosilyl) methane,-   1,2-bis(diphenylchlorosilyl)ethane,-   1,3-bis(diphenylchlorosilyl)propane,-   1,4-bis(diphenylchlorosilyl)butane,-   1,4-bis(diphenylchlorosilyl)benzene,-   bis(diphenylfluorosilyl)methane,-   1,2-bis(diphenylfluorosilyl)ethane,-   1,3-bis(diphenylfluorosilyl)propane,-   1,4-bis(diphenylfluorosilyl)butane,-   1,4-bis(diphenylfluorosilyl)benzene,-   bis(diphenylbromosilyl)methane,-   1,2-bis(diphenylbromosilyl)ethane,-   1,3-bis(diphenylbromosilyl)propane,-   1,4-bis(diphenylbromosilyl)butane,-   1,4-bis(diphenylbromosilyl)benzene,-   bis(diphenylhydrosilyl)methane,-   1,2-bis(diphenylhydrosilyl)ethane,-   1,3-bis(diphenylhydrosilyl)propane,-   1,4-bis(diphenylhydrosilyl)butane, and-   1,4-bis(diphenylhydrosilyl)benzene.

These compounds may be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (11) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof include tetrachlorosilane,tetrafluorosilane, and tetrabromosilane. These compounds may be usedalone or in combination of 2 or more.

The silicon compound expressed by the structural formula (12) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof includemethyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane,isopropyltrichlorosilane, butyltrichlorosilane,tert-butyltrichlorosilane, phenyltrichlorosilane, trichlorosilane,methyltrifluorosilane, ethyltrifluorosilane, triethylfluorosilane,propyltrifluorosilane, isopropyltrifluorosilane, butyltrifluorosilane,tert-butyltrifluorosilane, phenyltrifluorosilane, trifluorosilane,methyltribromosilane, ethyltribromosilane, propyltribromosilane,isopropyltribromosilane, butyltribromosilane, tert-butyltribromosilane,phenyltribromosilane, tribromosilane, and dibromosilane. These compoundsmay be used alone or in combination of 2 or more.

The silicon compound expressed by the structural formula (13) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples include dimethyldichlorosilane,diethyldichlorosilane, dipropyldichlorosilane,diisopropyldichlorosilane, dibutyldichlorosilane,di-tert-butyl-dichlorosilane, diphenyldichlorosilane,dimethylphenylchlorosilane, phenylethyldichlorosilane,phenylpropyldichlorosilane, phenylisopropyldichlorosilane,phenylbutyldichlorosilane, phenyl-tert-butyl-dichlorosilane,phenylmethyldichlorosilane, dichlorosilane, methyldichlorosilane,ethyldichlorosilane, propyldichlorosilane, isopropyldichlorosilane,butyldichlorosilane, tert-butyl-dichlorosilane, diphenyldichlorosilane,dimethyldifluorosilane, diethyldifluorosilane, dipropyldifluorosilane,diisopropyldifluorosilane, dibutyldifluorosilane,di-tert-butyldifluorosilane, diphenyldifluorosilane,phenylmethyldifluorosilane, phenylethyldifluorosilane,phenylpropyldifluorosilane, phenylisopropyldifluorosilane,phenylbutyldifluorosilane, phenyl-tert-butyl-difluorosilane,di-fluorosilane, methyldifluorosilane, ethyldifluorosilane,propyldifluorosilane, isopropyldifluorosilane, butyldifluorosilane,tert-butyl-difluorosilane, diphenyldifluorosilane,dimethyldibromosilane, diethyldibromosilane, dipropyldibromosilane,diisopropyldibromosilane, dibutyldibromosilane,di-tert-butyl-dibromosilane, diphenyldibromosilane,phenylmethyldibromosilane, phenylethyldibromosilane,phenylpropyldibromosilane, phenylisopropyldibromosilane,phenylbutyldibromosilane, phenyl-tert-butyl-dibromosilane,methyldibromosilane, ethyldibromosilane, propyldibromosilane,isopropyldibromosilane, butyldibromosilane, tert-butyl-dibromosilane,and diphenyldibromosilane. These compounds may be used alone or incombination of 2 or more.

The silicon compound expressed by the structural formula (14) is notparticularly limited, and may be appropriately selected in accordancewith the object. Specific examples thereof includetrimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane,triisopropylchlorosilane, tributylchlorosilane,tri-tert-butyl-chlorosilane, triphenylchlorosilane,diphenylmethylchlorosilane, diethylphenylchlorosilane,diphenylethylchlorosilane, dipropylphenylchlorosilane,diphenylpropylchlorosilane, diisopropylphenylchlorosilane,diphenylisopropylchlorosilane, dibutylphenylchlorosilane,dibutylmethylchlorosilane, di-tert-butyl-phenylchlorosilane,diphenyl-tert-butyl-chlorosilane, monochlorosilane, methylchlorosilane,ethylchlorosilane, propylchlorosilane, isopropylchlorosilane,butylchlorosilane, tert-butyl-chlorosilane, phenylchlorosilane,methylphenylchlorosilane, isopropylphenylchlorosilane,butylphenylchlorosilane, tert-butyl-phenylchlorosilane,trimethylfluorosilane, tripropylfluorosilane, triisopropylfluorosilane,tributylfluorosilane, tri-tert-butyl-fluorosilane,triphenylfluorosilane, dimethylphenylfluorosilane,diphenylmethylfluorosilane, diethylphenylfluorosilane,diphenylethylfluorosilane, dipropylphenylfluorosilane,diphenylpropylfluorosilane, diisopropylphenylfluorosilane,diphenylisopropylfluorosilane, dibutylphenylfluorosilane,dibutylmethylfluorosilane, di-tert-butyl-phenylfluorosilane,diphenyl-tert-butyl-fluorosilane, monofluorosilane, methylfluorosilane,ethylfluorosilane, propylfluorosilane, isopropylfluorosilane,tert-butyl-fluorosilane, butyffluorosilane, phenylfluorosilane,methylphenylfluorosilane, ethylphenylethoxysilane,propylphenylethoxysilane, isopropylphenylfluorosilane,butylphenylfluorosilane, tert-butyl-phenylfluorosilane,trimethylbromosilane, triethylbromosilane, tripropylbromosilane,triisopropylbromosilane, tributylbromosilane,tri-tert-butyl-bromosilane, triphenylbromosilane,dimethylphenylbromosilane, diphenylmethylbromosilane,diethylphenylbromosilane, diphenylethylbromosilane,dipropylphenylbromosilane, diphenylpropylbromosilane,diisopropylphenylbromosilane, diphenylisopropylbromosilane,dibutylphenylbromosilane, dibutylmethylbromosilane,di-tert-butyl-phenylbromosilane, diphenyl-tert-butyl-bromosilane,monobromosilane, methylbromosilane, ethylbromosilane, propylbromosilane,isopropylbromosilane, butylbromosilane, tert-butyl-bromosilane,phenylbromosilane, methylphenylbromosilane, ethylphenylethoxysilane,propylphenylethoxysilane, isopropylphenylbromosilane,butylphenylbromosilane, and tert-butyl-phenylbromosilane. Thesecompounds may be used alone or in combination of 2 or more.

As the method of synthesizing the silicone polymer, there is noparticular limitation to the reaction conditions or the like, and themethod may be appropriately selected in accordance with the object, aslong as a hydrolysis condensation polymerization reaction of at leastone of silicon compounds expressed by the general formulas (1) to (3),and at least one of the silicon compounds expressed by the generalformulas (4) to (7). Preferably, an alkali or acidic aqueous solution isused as a catalyzer.

The pH of the acidic and alkali acqueous solution is not particularlylimited, and may be appropriately selected in accordance with theobject. Preferably, the pH of the solution is 1 to 11.

If the pH of the solution exceeds 11, there may be a breakdown of asiloxane bond.

The acidic or alkali aqueous solution is not particularly limitated, andmay be appropriately selected in accordance with the object. Examplesthereof include hydrochloric acid, nitric acid, sulfuric acid, toulenesulfonic acid, oxalic acid, maleic acid, formic acid, acetic acid,ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. As theacidic aqueous solution, it is preferable not to use a hydrofluoricbecause there may be a breakdown of a siloxane bond.

In the hydrolysis condensation polymerization reaction, thecopolymerization ratio of the silicon compounds is not particularlylimited, and may be appropriately selected in accordance with theintended use of the silica film. For example, in the case of using asilica film as a protective film at the time of chemical mechanicalpolishing (CMP), since there is the requirement of chemical resistanceand adhesiveness to an underlying layer in addition to the mechanicalstrength, it is preferable to use, in the copolymerization ratio of 1:5,the combination of at least one of the silicon compounds expressed bythe general formulas (1) to (3), which contain hydrocarbon or aromatichydrocarbon in its skeleton and provide the silocone polymer with thechemical resistance and the moisture resistance, and at least one of thesilicon compounds expressed by the general formulas (4) to (7), whichprovide the silicone polymer with the mechanical strength and theadhesion property. More preferably, the combination of the siliconcompounds expressed by the structural formulas (8) and (11) may be usedin the copolymerization ratio of 1:2, which can provide the siliconepolymer with a more improved mechanical strength and adhesion property.

In addition, in the case where the silica film is used as a hard maskduring a dry etching in the manufacturing process of a multiplelayerwiring structure, or as an intermediate layer of a multilayer resist, itis preferable to adjust an etching selectivity by appropriately changingthe amount of the silicon compounds expressed by the general formulas(4) to (7) relative to the silicon compounds expressed by the generalformulas (1) to (3) which contain a hydrocarbon or an aromatichydrocarbon in its skeleton and provide the silicone polymer with theetching resistance property.

Moreover, in the case of using the silica film as an intermediate layerof a multilayer resist, with the object of preventing the reflection oflight, is is desirable to use the silicon compounds having an aromatichydrocarbon in its skeleton. Alternatively, it is preferable tointroduce an aromatic hydrocarbon to the side chain of a siloxane bondin the silicone polymer.

The hydrolysis conreaction condition of the hydrolysis condensationpolymerization reaction is not particularly limited, and may beappropriately selected in accordance with the object. The reactiontemperature is desirably 30° C. to 80° C., and more desirably 35° C. to60° C. The agitation time is desirably 1 to 72 hours, and more desirably10 to 48 hours.

—Organic Solvent—

In case of forming a silica film using the silica film forming material,it is preferable to form the silica film by means of a coating in termsof ease of film formation, and the silica film forming materialdesirably includes an organic solvent.

The organic solvent is not particularly limited as long as the siliconepolymer is soluble therein, and may be appropriately selected inaccordance with the object. Examples thereof include alcohols such asmethylalcohol, ethylalcohol, propylalcohol, isopropylalcohol,butylalcohol, isobutylalcohol, and tert-butylalcohol; phenols such asphenol, cresol, diethyiphenol, triethyiphenol, propyiphenol,phenylphenol, vinylphenol, allylphenol, and nonylphenol; ketones such ascyclohexanone, methylisobutylketone, and methylethylketone; celosolvessuch as methylcelosolve, and ethylcelosolve; hydrocarbons such ashexane, octane, decane; and glycols such as propyleneglycol,propyleneglycolmonomethylether, andpropyleneglycolmonomethyletheracetate. These are used alone or incombination of 2 or more.

—Other Components—

Other components is not particularly limited as long as it does notinfringe the effects of the present invention, and may be appropriatelyselected corresponding to the object. For example, various knownadditives may be provided.

The conten of other components in the silica film forming material maybe appropriately selected corresponding to types and contents of thesilicon compounds expressed by the general formulas (1) to (7), theorganic solvents and the like.

The silica film forming material according to the present inventioncomprises a silicone polymer that comprises, as part of its structure,CHx, an Si—O—Si bond, an Si—CH₃ bond, and an Si—CHx- bond, where the xindicates an integer of 0 to 2, and the silicone polymer is obtained bythe hydrolysis condensation polymerization reaction of at least one thesilicon compounds expressed by the general formulas from (1) to (3)having superior etching resistance and chemical resistance, and at leastone of the silicon compounds expressed by the general formulas (4) to(7) having superior adhesion property. Thus, the silicone polymer excelsin all properties of etching resistance, chemical resistance, moistureresistance, and adhesion property, making it possible to form a silicafilm with a low dielectric constant, which is suitable for use in themethod of manufacturing the silica film of the present invention, themultilayer wiring structure of the present invention, and thesemiconductor device of the present invention, described below.

(Silica Film and the Method of Manufacturing the Same)

The silica film according to the present invention is obtained by themethod of manufacturing the silica film according to the presentinvention.

The method of manufacturing the silica film of the present inventioncomprises: coating the silica film material of the present inventiononto the surface to be processed; and heating the surface to beprocessed, and further includes any other processes if needed.

Hereafter, the details of the silica film of the present invention willbe made clear through the explanation of the method of manufacturing thesilica film of the present invention.

<Coating Process>

In the coating process, the silica film forming material of the presentinvention is coated onto the surface to be processed.

The detail of the silica film forming material is given as describedabove.

The coating method is not particularly limited, and may be appropriatelyselected in accordance with the object. For instance, a spin coatingmethod, a dip coating method, a kneader coating method, a curtaincoating method, a blade coating method, and the like can be given asexamples. Among these examples, a spin coating and a dip coating arepreferred when considering coating efficiency and the like. In case of aspin coating method, as an example of the coating conditions, a rotationspeed is 100 rpm to 10,000 rpm, preferably, 800 rpm to 5,000 rpm, and acoating time is 1 second to 10 minutes, preferably 10 seconds to 90seconds.

The surface to be processed is not particularly limited, and may beappropriately selected in accordance with the object. In the case offorming the silica film in a semiconductor device, the surface to beprocessed may be a semiconductor substrate. Specific examples of thesemiconductor substate include a substate such as a silicon wafer,various oxide films, and low dielectric constant films such as poroussilica film and the like.

Through the above process, the silica film forming material of thepresent invention is coated onto the surface to be processed.

<Heating Process>

In the heating process, the silica film forming material coated onto thesurface to be processed is heated.

The heating method is not particularly limited, and may be appropriatelyselected in accordance with the object. Preferably, the organic solventis dried and the silica film forming material is baked.

In this case, the oxidation of a hydrocarbon, aromatic hydrocarbon, andothers, which has introduced to the side chain and skeleton of thesilicone polymer, can be suppressed.

Conditions such as temperature, atmosphere, and so forth may beappropriately selected in accordance with the object. Preferably, thetemperature is 50° C. to 400° C., more preferably, 80° C. to 350° C.

When the temperature is 50° C. or less, sufficient strength may not beobtained because the organic solvent remains in the film, and when thetemperature exceeds 400° C., there may be a breakdown of thesilicon-hydrocarbon bond of the side chain and skeleton in the siliconepolymer.

With regard to the atmosphere, if the heating is performed in the air,there is a fear of raising the dielectric constant due to taking inoxygen from the air. Therefore, the heating may be preferably performedin the presence of an iner gas or under a reduced pressure. Preferableexample of the inert gas includes a nitrogen gas.

Furthermore, in the case where the underlying layer of the silica filmis a porous silica film formed by, for instance, a spin coating method,the heating process may be performed at one time after coating amaterial of forming the porous silica film, drying a solvent, andcoating the silica film forming material on the porous silica film. Inthis case, a reduction in the cost to form the film can be devised.

<Other Processes>

Other processes are not particularly limited, and may be appropriatelyselected in accordance with the object. Examples thereof include apattern forming process.

The pattern forming process is for forming a pattern by selectivelyexposing and developing the silica film formed by the coating processand heating process described above.

The pattern forming process can be performed according to well-knownpattern forming methods.

In addition, baking treatment may be performed between the exposing anddeveloping in terms of accelerating the reaction.

Next, the method of manufacturing the silica film of the presentinvention will be described in detail. For example, in the coatingprocess, the silica film is formed by, first, coating the silica filmforming material of the present invention onto the surface to beprocessed (for example, a low dielectric constant film such as poroussilica film or the like) by a spin coating, and by heating at atemperature of 50 to 400° C. to dry the solvent, followed by baking.Consequently, the silica film of the present invention is formed. Inaddition, if exposing and developing the formed silica film according tothe above pattern forming process, a pattern of the silica film having adesired form is formed.

The method of manufacturing the silica film of the present invention canbe used suitably in various fields. Particularly, it can be preferablyused in the manufacturing of the silica film of the present inventiondescribed below.

The silica film of the present invention is not particularly limited inthe various characteristics of materials such as shape, structure, size,and so forth as long as the silica film includes the silicone polymerdescribed above, and may be appropriately selected in accordance withthe object. Preferably, the silica film has the following thickness,dielectric constant, etching resistance, chemical resistance, moistureresistance, adhesive strength, and so forth, which have the ability foruse in a multilayer wiring structure and a semiconductor device.

The verification method of the existence of the silicone polymer is notparticularly limited, and may be appropriately selected in accordancewith the object. For example, an infrared spectroscopic analysis can beused. The existence of the silicone polymer can be verified by, forexample, measuring the absorption peaks of CHx, Si—O—Si bond, Si—CH₃bond, and Si—CHx- bond, and by analyzing to confirm that all of thesestructures are contained.

The form of the silica film is not particularly limited, and may beappropriately selected in accordance with the object. Examples of theform of the silica film include a solid film form, which is formed onthe entire surface of the surface to be processed, and a patterned form.

Example of a method of forming the silica film having the solid filmform include a method in which a base material having the surface to beprocessed is immersed into the silica film forming material of thepresent invention to form the entire surface of the base materialsurface (the surface to be processed).

Examples of a method of forming the silica film having the patternedform include:

a method in which the surface to be processed is patterned to have, forexample, a line form, by using a resist, and the silica film formingmaterial is coated therein; and

a method in which a silica film of a solid film form is formed on thesurface to be processed, a resist is coated and patterned to have adesired resist pattern, and then the a wet or dry etching is performed.

The structure of the silica film is not particularly limited, and may beappropriately selected in accordance with the object. For example, itmay be a monolayer structure or a multilayer structure.

When the silica film has a patterned form or a multilayer structure, thedielectric constant in each portion of the patterned form or in eachlayer of the multilayer structure may be the same, or may berespectively different.

The size of the silica film is not particularly limited, and may beappropriately selected in accordance with the object. For example, whenthe silica film is used in the multilayer wiring structure, asemiconductor device, or the like, the size is preferred to correspondto the size of the existing semiconductor devices.

The thickness of the silica film is not particularly limited, and may beappropriately selected in accordance with the object. For example, whenthe silica film is used in multilayer wiring structure, a semiconductordevice, and so forth, the thickness is normally 10 nm to 1 μm,preferably, 10 nm to 500 nm, more preferably, 10 nm to 300 nm from theperspective of its structure.

When the thickness is less than 10 nm, a structural defect such aspinholes may be created, and when the thickness exceeds 500 nm, theetching selectivity relative to the resist pattern may not besufficiently obtained upon a dry etching.

The dielectric constant is not particularly limited, and may beappropriately selected in accordance with the object. It is preferably3.0 or less, more preferably, 2.8 or less.

In addition, the dielectric constant can be measured by, for example,using a dielectric measuring device by forming gold electrodes on thesilica film.

The etching resistance property can be evaluated by the etching rate.The etching rate is not particularly limited, and may be appropriatelyselected in accordance with the object. However, the etching ratechanges depending on gas types, pressure, voltage, and so forth. Forexample, when CF₄/CHF₃ gas is used as the etching gas, the ratio of theetching rate of the silica film to the etching rate of the lowdielectric constant film (for example, the porous silica film) ispreferred to be from 1:1.5 to 1:10.0.

In addition, the etching rate can be measured as followed. Specifically,a sample is etched for a predetermined time by using a well-knownetching device, and then the decreased film amount of the sample ismeasured to calculate the decreased amount per unit time.

The chemical resistance of the silica film is not particularly limited,and may be appropriately selected in accordance with the object.Preferably, the etching rate at the time of immersing in the 0.5 mass %HF is 1 nm/min to 100 nm/min.

The moisture resistance of the silica film is not particularly limited,and may be appropriately selected in accordance with the object. Forexample, in the case where the silica film is left to stand for one weekat a room temperature, and a capacity of the silica film is measured byusing a probe which is connected to an AC power of 1 MHz, 1 V, thechange in the dielectric constant, which is calculated based on themeasured capacity and the film thickness of the silica film, ispreferably 0.3 or less, more preferably 0.2 or less.

The adhesive strength of the silica film is not particularly limited,and may be appropriately selected in accordance with the object. Forexample, the strength measured by, for example the adhesive strengthmeasuring device (“Sebastian Five” manufactured by Quad Group) ispreferred to be larger than 5.88 GPa (600 kgf/mm²).

The silica film of the present invention, because of a low dielectricconstant, can be used favorably as an insulation layer, and also can beused as a general low dielectric constant film (interlayer insulationfilm) itself, or used as a protective to be formed on the surface of thelow dielectric constant film. Especially, the silica film of the presentinvention has the ability to be used as the protective film because itis superior in the etching resistance, chemical resistance, moistureresistance, as well as the adhesive property. For this reason, thesilica film of the present invention can be used favorably as a hardmask during a dry etching in the method of manufacturing a multilayerwiring structure of the present invention and the method ofmanufacturing a semiconductor device of the present invention describedlater, and in this case, a fine wiring pattern can be formed with highprecision.

The silica film having excellent chemical resistance can be suitablyused as a protective film during a chemical mechanical polishing (CMP).In such a case, those portions other than those portions not to bepolished are protected thereby enabling highly precise polishing.

The silica film of the present invention excels in etching resistance,chemical resistance, and moisture resistance, and the adhesive propertyare favorable. Moreover, it has the low dielectric constant and cancontribute to a higher response speed, and therefore, this is suitableto the semiconductor device such as a multilayer wiring structure, asemiconductor integrated circuit, and so forth that require higherresponse speeds, and is especially suitable to the following multilayerwiring structure of the present invention and the semiconductor deviceof the present invention.

(Multilayer Wiring Structure and Method of Manufacturing the Same)

The multilayer wiring structure of the present invention includes atleast the silica film of the present invention.

The method of manufacturing a multilayer wiring structure of the presentinvention is a method for manufacturing the multilayer wiring structureof the present invention described above. The method of manufacturing amultilayer wiring structure includes at least a silica film formingprocess and a wiring structure forming process, and further includesother processes which are selected suitably according to necessity.

Hereinafter, the details of the multilayer wiring structure of thepresent invention will be made clear through the description of themethod of manufacturing the multilayer wiring structure of the presentinvention.

<Silica Film Forming Process>

In the silica film forming process, the silica film forming material ofthe present invention is coated onto the surface to be processed andthen heated the surface to be processed so as to form the silica film.

The silica film forming process can be performed favorably by the methodof manufacturing the silica film of the present invention.

In addition, the details regarding the surface to be processed, thecoating, and others are as stated above.

The heating method is not particularly limited, and may be appropriatelyselected in accordance with the object. Preferably, the organic solventis dried and the silica film forming material is baked. In this case,the oxidation of a hydrocarbon, aromatic hydrocarbon, and others, whichhas introduced to the side chain and skeleton of the silicone polymer,can be suppressed.

Conditions such as temperature, atmosphere, and so forth may beappropriately selected in accordance with the object. Preferably, thetemperature is 50° C. to 400° C., more preferably, 80° C. to 350° C.

When the temperature is 50° C. or less, sufficient strength may not beobtained because the organic solvent remains in the film, and when thetemperature exceeds 400° C., there may be a breakdown of thesilicon-hydrocarbon bond of the side chain and skeleton in the siliconepolymer.

With regard to the atmosphere, if the heating is performed in the air,there is a fear of raising the dielectric constant due to taking inoxygen from the air. Therefore, the heating may be preferably performedin the presence of an inner gas or under a reduced pressure. Preferableexample of the inert gas includes a nitrogen gas.

Furthermore, in the case where the underlying layer of the silica filmis a film (for example, a low dielectric constant film such as a poroussilica film) formed by, for instance, a spin coating method, the heatingprocess may be performed at one time after coating a material of formingthe low dielectric constant film, drying a solvent, and coating thesilica film forming material on the low dielectric constant film. Inthis case, a reduction in the cost to form the film can be devised.

<Wiring Structure Forming Process>

In the wiring forming process, a wiring structure is formed.

When the multilayer wiring structure is formed, the wiring structureforming process is preferred to include other processes which areappropriately selected such as the through-via forming process and theconductor plating process.

—Through-Via Forming Process—

In the through-via forming process, a through-via is formed in order toconnect to the wiring formed at the uppermost layer of the silica filmthat is formed on the surface to be processed.

Forming the through-via is performed by irradiating the laser beam withthe appropriate exposure amount on the portion of the through-via.

The laser bean is not particularly limited and may be appropriatelyselected in accordance with the object, and for example, a carbondioxide gas laser, an eximer laser, a YAG laser, or the like can begiven.

—Conductor Plating Process—

In the conductor plating process, a conductor plating layer is formed bycoating a conductor as the wiring precursor on the entire surface of thesilica film formed on the surface to be processed.

The conductor plating can be performed by using an ordinary platingmethod such as, for example, non-electrolytic plating, electrolyticplating or the like.

Formation of the wiring structure is accomplished by etching theconductor plating layer formed by the conductor plating process so as tohave the desired wiring pattern.

The etching method is not particularly limited, and may be appropriatelyselected in accordance with the object, and an ordinary etching methodcan be used.

The wiring structure is formed by the process stated above.

Repeating the series of processes as necessary of the silica filmforming process and the wiring forming process (including thethrough-via forming process and the conductor plating process) makes itpossible to manufacture the multilayer wiring structure which has a highdegree of circuit integration.

The method of manufacturing the multilayer wiring structure of thepresent invention can be suitably used in various fields. Particularly,it is suited for use in the manufacturing of the multilayer wiringstructure of the present invention given hereafter.

The multilayer wiring structure of the present invention excels inetching resistance, chemical resistance, moisture resistance, and theadhesive property, and includes the silica film of the presentinvention, which has a low dielectric constant, on the low dielectricconstant film, the parasitic capacity can be reduced and it is possibleto increase the signal propagation speed, making it favorable for asemiconductor device, in which higher response speeds are demanded, suchas a semiconductor integrated circuit or the like, and especiallyfavorable for a semiconductor device of the present invention asdescribed below.

(Semiconductor Device and Method of Manufacturing the Same)

The semiconductor device of the present invention comprises the silicafilm of the present invention as either an interlayer insulation film ora protective film formed on the surface of the interlayer insulationfilm.

The method of manufacturing a semiconductor device of the presentinvention is the method for manufacturing the semiconductor device ofthe present invention described above, which includes at least a silicafilm forming process and a patterning process, as well as any processappropriately selected as necessary.

Hereinafter, the details of the semiconductor device of the presentinvention will be made clear through the description of the method ofmanufacturing the semiconductor device of the present invention.

<Silica Film Forming Process>

In the silica film forming process, the silica film is formed on thesurface to be processed, using the silica film forming material of thepresent invention.

Moreover, the details of the surface to be processed, the silica filmforming material, and others are as described above.

In the silica film forming process, preferably, the silica film formingmaterial of the present invention is coated onto the surface to beprocessed, and then heated the surface to be processed, which may besuitably performed according to the method of manufacturing the silicafilm of the present invention. Moreover, the method for coating is asdescribed in the explanation of the method of manufacturing the silicafilm of the present invention.

The heating method is not particularly limited, and may be appropriatelyselected in accordance with the object. Preferably, the organic solventis dried and the silica film forming material is baked. In this case,the oxidation of a hydrocarbon, aromatic hydrocarbon, and others, whichhas introduced to the side chain and skeleton of the silicone polymer,can be suppressed.

Conditions such as temperature, atmosphere, and so forth may beappropriately selected in accordance with the object. Preferably, thetemperature is 50° C. to 400° C., more preferably, 80° C. to 350° C.

When the temperature is 50° C. or less, sufficient strength may not beobtained because the organic solvent remains in the film, and when thetemperature exceeds 400° C., there may be a breakdown of thesilicon-hydrocarbon bond of the side chain and skeleton in the siliconepolymer.

With regard to the atmosphere, if the heating is performed in the air,there is a fear of raising the dielectric constant due to taking inoxygen from the air. Therefore, the heating may be preferably performedin the presence of an iner gas or under a reduced pressure. Preferableexample of the inert gas includes a nitrogen gas.

Furthermore, in the case where the underlying layer of the silica filmis a film (for example, a low dielectric constant film such as a poroussilica film) formed by, for instance, a spin coating method, the heatingprocess may be performed at one time after coating a material of formingthe low dielectric constant film, drying a solvent, and coating thesilica film forming material on the low dielectric constant film. Inthis case, a reduction in the cost to form the film can be devised.

<Patterning Process>

In the patterning process, the surface to be processed is patterned byway of etching by using the silica film obtained by the silica filmforming process as an etching mask.

With this patterning process, preferably, after the desired pattern isformed by performing selectively exposing and development the silicafilm, the etching is performed by using the formed pattern. In thiscase, the etching can be performed easily to form the desired patternform.

The pattern can be formed according to known patterning methods.

Moreover, baking treatment can be performed in between the exposing anddeveloping from the perspective of promoting the reaction.

The etching method is not particularly limited, and may be appropriatelyselected in accordance with the object. For example, a dry etching andwet etching can be given as suitable examples. Since the silica film ofthe present invention excels in etching resistance, chemical resistance,moisture resistance, and adhesion with the underlying layer, thepatterning can be performed with high precision.

<Other Processes>

Other processes are not particularly limited, and may be appropriatelyselected in accordance with the object, and the wiring structure formingprocess can be given as an example.

The wiring structure forming process is a process for forming wiringstructure, and the details thereof are as given in the explanation ofthe manufacturing method of the multilayer wiring structure.

Repeating this series of processes as necessary of the silica filmforming process, patterning process, and the wiring structure formingprocess (including the aforementioned through-via forming process andthe conductor plating process) can manufacture a semiconductor devicehaving a multilayer wiring structure with a high degree of circuitintegration.

An example of the semiconductor device of the present invention isexplained hereafter with reference to the drawings.

The semiconductor device of the present invention can be obtained, forexample, in the following manner. First, as shown in FIG. 1A, atransistor, which has a source diffusion layer 5 a, a drain diffusionlayer 5 b, and a side wall insulation film 3 and is separated byinter-element separation film 2, is formed on a silicon wafer 1. Then,as shown in FIG. 1B, a interlayer insulation film 6 (phosphorus glass)and a stopper film 7 (SiC) is formed on the silicon wafer 1, and then acontact hole for extracting an electrode is formed. As shown in FIG. 1C,after forming the barrier film 8 (TiN) by way of sputtering to have athickness of 50 nm, a tungsten (W) conductor plug 9 (blanket) is filledin the contact hole by mixing WF₆ gas and hydrogen gas and performing areduction to form a via, and portions other than the via is removed byway of chemical mechanical polishing (CMP).

Further, as shown in FIG. 1D, an SiC:O:H film 10 is formed to have athickness of 30 nm on the stopper film 7 on which the via was formed,and a porous silica film (low dielectric constant film; wiringseparation insulating film) 11 is formed thereon so as to have athickness of 160 nm, and a silica film 12 of the present invention isformed on the porous silica film, using the silica film forming materialof the present invention, so as to have a thickness of 30 nm. Further,as shown in FIG. 1E, the silica film 12 is processed by way of the Fplasma method with CF₄/CHF₃ gas as the source material, using the resistlayer as a mask having a pattern of a first wiring layer with a wiringwidth of 100 nm and a space of 100 nm, thereby forming a wiring trench.Then, as shown in FIG. 1F, a barrier film 13 (TaN) is formed in thewiring trench by way of sputtering method to have a thickness of 10 nmto prevent the diffusion of the wiring material (copper) into the poroussilica film 11. Next, a seed layer (Cu), which functions as an electrodeat the time of electrolytic plating, is formed on the surface of theburrier film 13 formed in the wiring trench, by way of sputtering methodto a thickness of 10 nm. Next, a copper wiring 14 (Cu) is deposited tohave a thickness of 600 nm by way of the electrolytic plating, and thenthe copper is removed except for the wiring pattern portions by way ofchemical mechanical polishing (CMP). Then, a stopper film (diffusionprevention film) 15 formed of an SiC:O:H film is formed on the copperwiring 14 (Cu) to have a thickness of 30 nm, thereby forming a firstwiring layer (copper). Here, the stopper film (diffusion preventionfilm) 15 is formed by way of the plasma CVD method by using silane gasand ammonia gas to prevent the diffusion of the wiring material (copper)into the porous silica film 11.

Next, as shown in FIG. 1G, the porous silica film (low dielectricconstant film; wiring separation insulating film, SiOC film) 16 isformed on the stopper film (diffusion prevention film) 15 to have athickness of 180 nm. Then, a silica film 17 of the present invention isformed on the porous silica film 16 to have a thickness of 30 nm byusing the silica film forming material of the present invention.Further, as shown in FIG. 1H, a porous silica film (low dielectricconstant film) 18 is formed on the silica film 17 to have a thickness of160 nm, and the silica film 19 of the present invention is formed so asto have a thickness of 30 nm by using the silica film forming materialof the present invention.

Then, as shown in FIG. 1I, a via is formed in these insulation films byusing a resist layer having a via pattern as a mask. Specifically, thesilica film 19, the porous silica film 18, the silica film 17, and theporous silica film 16 are processed in this order by way of the F plasmamethod with CF₄/CHF₃ gas as the source material, and changing the gascomposition and pressure. Next, a wiring trench is formed by way of theF plasma method using CF₄/CHF₃ gas as the source material by using aresist layer having a pattern of a second wiring layer as a mask. Then,as shown in FIG. 1J a barrier film (TaN) 20 for preventing the diffusionof the wiring material (copper) into the porous silica film 18 is formedin the via and the wiring trench by way of sputtering method to have athickness of 10 nm. Next, a seed layer (Cu), which functions as anelectrode at the time of electrolytic plating, is formed to have athickness of 10 nm on the surface of the barrier film 20 formed in thewiring trench. Next, a copper wiring 21 (Cu) is deposited by way of theelectrolytic plating method so as to be a thickness of 1,400 nm, andthen the copper is removed except for the wiring pattern portions by wayof chemical mechanical polishing (CMP). Further, as shown in FIG. 1K, anSiC:O:H film 22 is formed to have a thickness of 30 nm by way of theplasma CVD method, thereby forming a second via and wiring layer(copper).

A third via and wiring layer (copper) is formed by the same manner as inthe second via and wiring layer described above, whereby a semiconductordevice having a third layer copper-wiring structure, which correspondsto a multilayer wiring structure of the present invention, can bemanufactured.

The method of manufacturing the semiconductor device of the presentinvention can be suitably used in the manufacture of a semiconductordevice having multilayer wiring structure. Further, a high performancesemiconductor device can be efficiently manufactured which achieves thereduction of wiring resistance and the reduction of parasiticinter-wiring capacity, and high speed increase of signal propagationspeed becomes possible. The method of manufacturing the semiconductordevice is especially suitable to the manufacture of the semiconductordevice of the present invention which has the silica film of the presentinvention as an interlayer insulating film, protective film, or thelike.

The semiconductor device of the present invention has a silica film ofthe present invention which is formed by using the silica film formingmaterial of the present invention as a protective film which is formedon the interlayer insulation film or on the surface of the interlayerinsulation film. The silica film of the present invention has a lowdielectric constant. Therefore, when using the silica film as aninterlayer insulating film in a semiconductor device, a semiconductordevice having high reliability and a high speed and capable of achievinga reduction in wiring resistance and a reduction in parasiticinter-wiring capacity while being superior in insulation propertiesbetween each layer can be obtained. Further, the silica film is superiorin etching resistance, chemical resistance, moisture resistance, andadhesion. Therefore, when using the silica film as a protective film, itis possible to protect the interlayer insulation and to form finewirings.

The semiconductor device of the present invention is especially suitableas, for example, flash memory, DRAM, FRAM, MOS transistor, or the like.

EXAMPLES

Examples of the present invention will be described below, however, thepresent invention is not limited to the following examples.

Examples 1 to 27

—Preparation of Silica Film Forming Material—

Into a 4-mouth flask, 1,2-bis(dimethylethoxysilyl)ethane (1,2-DMESE) and1,4-bis(dimethylethoxysilyl)benzene(1,4-DMESB), which are the siliconcompounds expressed by the structural formula (3); tetraethoxysilane(TEOS) which is the silicon compound expressed by the structural formula(4); and methyltriethoxysilane (MTEOS) and phenyltriethoxysilane(PTEOS), which are the silicon compounds expressed by the structuralformula (5); 500 ppm nitric acid water; and propyleneglycolmonomethylether as the organic solvent were poured in the amountsshown in Tables 1 to 3, respectively, and hydrolysis condensationpolymerization reaction was performed over a 2 hour period at 50° C.,thereby preparing the silica film forming materials.

—Manufacturing Silica Film—

Each silica film forming material thus obtained was coated onto thesilicon wafer by way of spin coating at 1,500 rpm of rotation speed for1 minute so as to have a thickness of 1 μm. Next, each silicon wafer wasplaced on a hotplate set at a temperature of 150° C. to dry the organicsolvent for 3 min under N₂ gas atmosphere. Further, each silicon waferwas baked for 30 min under N₂ gas atmosphere by using an electricfurnace set at the temperature of 400° C., thereby manufacturing thesilica films.

The existence of silicone polymer in the silica film thus obtained wasverified by infrared spectroscopic analysis. FIG. 2 shows thecomposition of the polymer in the silica film of Example 1. According toFIG. 2, the existence of CHx, Si—O—Si bond, Si—CH₃ bond, and Si—CHx-bond can be verified in the silica film of Example 1, and it can befound that the silica film of the Example 1 includes the siliconepolymer having all of these constructions.

<Measurement of Dielectric Constant>

A gold electrode of 1 mm diameter was formed on each silica film thusobtained, followed by measuring the capacity by using a probe connectedto AC power of 1 MHz, 1V. The dielectric constant was calculated basedon the measured capacity and the film thickness. The results are shownin Tables 1 through 3.

<Measurement of Adhesion>

A porous silica film (low dielectric constant film, “Celamate NCS” madeby Shokubai Kasei) was formed on a silicon substrate. Then, the silicafilm forming materials of Examples 1 to 27 were coated on the siliconsubstrate by way of spin coating at 1,500 rpm for 1 min as to be 0.2 μmin thickness, respectively. Next, each silicon substrate was placed on ahot plate set at 150° C. to dry the organic solvent for 3 min under N₂gas atmosphere. Further, each silicon substrate was baked under N₂ gasatmosphere for 30 min by using an electric furnace set at a temperatureof 400° C., thereby manufacturing the lamination layers each having thesilica film and the porous silica film laminated the silica film.

With respect to each lamination layer thus obtained, the adhesionstrength to the porous silica film and silica film was measured using anadhesion strength measuring instrument (“Sebastian Five” made by theQuad Group). The results are shown in Tables 1 through 3.

<Measurement of Etching Rate>

Dry etching was performed to each lamination layer by F plasma withCF₄/CHF₃ gas as the source material, and the etching rate of the poroussilica film and the silica film was measured. The results are shown inTables 1 through 3.

<Evaluation of Etching Resistance>

Silica films of a thickness of 400 nm were formed by using the silicafilm forming materials of Examples 1 to 27 after respectively forming anovolak resin films of 150 nm thickness onto a silicon substrate. Thewiring pattern with a 200 nm pitch was formed on each silica film byexposing and developing the silica film using an ArF resist. Then, across-section of each silica film was observed using a scanning electronmicroscope (SEM) (made by Hitachi, Ltd.) to verify the resist patternform. The results are shown in Tables 1 through 3.

Next, a dry etching was performed by F plasma with CF₄/CHF₃ gas as thesource material to the silica films each having a good resist pattern,and the etching shift amount was respectively measured by way of theSEM. The results are shown in Tables 1 through 3.

Moreover, the etching shift amount indicates the amount of displacementin the actual etching size as compared to the predetermined etchingsize.

<Evaluation of Chemical Resistance and Moisture Resistance>

The evaluation of the chemical resistance was performed by measuring theetching rate when etching the silica films with a 0.5 mass % HF.Specifically, the silica film forming materials of Examples 1 to 27 werecoated onto a silicon substrate by way of spin coating at 1,500 rpm for1 min so as to be 1 μm in thickness, respectively. Next, each siliconsubstrate was placed on a hotplate set at 150° C. to dry the organicsolvent for 3 min under N₂ gas atmosphere. Further, each siliconsubstrate was baked under N₂ gas atmosphere for 30 min by using anelectric furnace set at a temperature of 400° C., thereby forming thesilica films. Each silicon substrate having the silica film formedthereon was then immersed in 0.5 mass % HF for 1 min and a wet etchingwas performed, and the etching rate was calculated by measuring thereduced film amount.

The evaluation of the moisture resistance was performed by measuring thechange in the dielectric constant between the dielectric constantimmediately after the formation of the silica film and that afterleaving to stand for 7 days. Specifically, the silica films of 150 nmthickness were formed by using the silica film forming materials ofExamples 1 to 27, in the same manner as in the evaluation of thechemical resistance described above. After each silica film was left tostand for 7 days at room temperature, the capacity was measured using aprobe connected to an AC power of 1 MHz, 1V. The dielectric constant wascalculated based on the measured capacity and the film thickness of thesilica film. The results are shown in Tables 1 through 3.

TABLE 1 Example No. 1 2 3 4 5 6 7 8 9 1,2-DMESE 0.1 0.1 0.1 0.15 0.150.15 0.1 0.1 0.1 (mol) 1,4-DMESB — — — — — — — — — (mol) TEOS (mol) 0.1— — 0.05 — — 0.05 0.05 — MTEOS (mol) — 0.1 — — 0.05 — 0.05 — 0.05 PTEOS(mol) — — 0.1 — — 0.05 — 0.05 0.05 500 ppm nitric 0.7 0.6 0.6 0.6 0.50.5 0.6 0.6 0.5 acid solution (mol) PGMEA (g) 200 200 200 200 200 200200 200 200 Dielectric 2.7 2.7 2.6 2.8 2.6 2.6 2.7 2.7 2.7 constant*Moisture 2.7 2.7 2.6 2.8 2.6 2.6 2.7 2.7 2.7 resistance** Chemical −32−16 −12 −27 −10 −14 −19 −15 −9 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:3 1:4 1:5 1:4 1:4 1:5 1:3 1:3 1:3 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 3 2 3 23 3 2 2 3 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

TABLE 2 Example No. 10 11 12 13 14 15 16 17 18 1,2-DMESE — — — — — — — —— (mol) 1,4-DMESB 0.1 0.1 0.1 0.15 0.15 0.15 0.1 0.1 0.1 (mol) TEOS(mol) 0.1 — — 0.05 — — 0.05 0.05 — MTEOS (mol) — 0.1 — — 0.05 — 0.05 —0.05 PTEOS (mol) — — 0.1 — — 0.05 — 0.05 0.05 500 ppm nitric 0.7 0.6 0.60.6 0.5 0.5 0.6 0.6 0.5 acid solution (mol) PGMEA (g) 200 200 200 200200 200 200 200 200 Dielectric 2.8 2.7 2.7 2.6 2.7 2.7 2.6 2.7 2.7constant* Moisture 2.8 2.7 2.7 2.6 2.7 2.7 2.6 2.7 2.7 resistance**Chemical −25 −12 −12 −19 −13 −18 −15 −15 −13 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:3 1:4 1:5 1:4 1:4 1:5 1:3 1:3 1:3 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 3 3 2 32 3 3 3 2 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

TABLE 3 Example No. 19 20 21 22 23 24 25 26 27 1,2-DMESE 0.05 0.05 0.050.075 0.075 0.075 0.05 0.05 0.05 (mol) 1,4-DMESB 0.05 0.05 0.05 0.0750.075 0.075 0.05 0.05 0.05 (mol) TEOS (mol) 0.1 — — 0.05 — — 0.05 0.05 —MTEOS (mol) — 0.1 — — 0.05 — 0.05 — 0.05 PTEOS (mol) — — 0.1 — — 0.05 —0.05 0.05 500 ppm nitric 0.7 0.6 0.6 0.5 0.5 0.5 0.7 0.7 0.6 acidsolution (mol) PGMEA (g) 200 200 200 200 200 200 200 200 200 Dielectric2.7 2.6 2.6 2.7 2.6 2.6 2.6 2.6 2.6 constant* Moisture 2.7 2.6 2.6 2.72.6 2.6 2.6 2.6 2.6 resistance** Chemical −27 −14 −18 −24 −18 −29 −21−25 −18 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:4 1:4 1:5 1:4 1:4 1:5 1:4 1:4 1:4 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 3 3 2 33 3 2 3 3 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

From the results of tables 1 to 3, it has been found that each silicafilm made by the silica film forming materials of Examples 1 to 27 haslow dielectric constant, does not change the dielectric constant evenafter seven days, has excellent moisture resistance, chemical resistanceand etching resistance (etching rate ratio) with a small amount ofetching shift, possesses resistance to both wet and dry etching, and hasgood adhesive strength.

Comparative Examples 1 to 8

The silica films of Comparative Examples were manufactured by preparingthe silica film forming materials in the same manner as in Example 1,except for using one of the following (a) and (b), in the amounts asshown in Table 4,

(a) 1,2-bis (dimethylethoxysilyl)ethane (1,2-DMESE) and 1,4-bis(dimethylethoxysilyl) benzene (1,4-DMESB), which are the siliconcompounds expressed by the structural formula (3), and

(b) at least one of tetraethoxysilane (TEOS) which is the siliconcompound expressed by the structural formula (4); andmethyltriethoxysilane (MTEOS) and phenyltriethoxysilane (PTEOS), whichare the silicon compounds expressed by the structural formula (5),

and except that the hydrolysis condensation polymerization reaction wasnot performed. Moreover, the characteristics of the respective silicafilms were evaluated in the same manner as in Example 1. The results arealso shown in Table 4.

In addition, the existence of silicone polymer in the silica film thusobtained was verified by infrared spectroscopic analysis. FIG. 2 showsthe composition of the polymer in the silica film of Comparative Example4. According to FIG. 2, the existence of CHx, Si—O—Si bond, Si—CH₃ bond,and Si—CHx- bond cannot be verified in the silica film of ComparativeExample 4, and it can be found that the silica film of the ComparativeExample 4 does not include the silicone polymer having all of theseconstructions.

TABLE 4 Comp. Example No. 1 2 3 4 5 6 7 8 1,2-DMESE — — — — — — 0.2 —(mol) 1,4-DMESB — — — — — — — 0.2 (mol) TEOS (mol) 0.2 — — 0.1 0.1 — — —MTEOS (mol) — 0.2 — 0.1 — 0.1 — — PTEOS (mol) — — 0.2 — 0.1 0.1 — — 500ppm nitric 0.8 0.6 0.6 0.7 0.7 0.6 0.7 0.7 acid solution (mol) PGMEA (g)200 200 200 200 200 200 200 200 Dielectric 4.8 3.2 3.2 4.1 3.9 3.3 2.72.8 constant* Moisture 5.6 3.8 3.3 4.3 4.2 3.4 2.7 2.9 resistance**Chemical −721 −436 −332 −530 −480 −392 −211 −134 resistance (nm/min)Adhesive >600 >600 520 480 440 330 260 190 strength (kgf/mm sq.) Etchingrate 1:1 1:1 1:2 1:1 1:1 1:2 1:15 1:15 ratio*** Resist form PatternPattern Good Pattern Good Good Good Good collapse collapse collapseEtching shift 21 15 6 14 12 8 Unopened Unopened (nm) *(dielectricconstant immediately after formation of silica film) **(dielectricconstant after leaving to stand for 7 days) ***(ratio of silica film toporous silica film)

From the results of table 4, it has been found that each silica filmmade by the silica film forming materials of Comparative Examples 1 to 8has high dielectric constant, increases further the dielectric constantafter seven days, has poor moisture resistance, chemical resistance andetching resistance (etching rate ratio) with a large amount of etchingshift, possesses low resistance to both wet and dry etching, and has lowadhesive strength.

Examples 28 to 54

—Preparation of Silica Film Forming Material—

Into a 4-mouth flask, 1,2-bis (dimethylchlorosilyl) ethane (1,2-DMCSE)and 1,4-bis(dimethylchlorosilyl)benzene(1,4DMCSB), which are the siliconcompounds expressed by the structural formula (10); tetrachlorosilane(TCS) which is the silicon compound expressed by the structural formula(11); methvltrichlorosilane (MTCS) and phenyltrichlorosilane (PTCS),which are the silicon compounds expressed by the structural formula(12); 500 ppm nitric acid water; and propylene glycolmonomethylether asthe organic solvent were poured in the amounts shown in Tables 5 to 7,respectively, and hydrolysis condensation polymerization reaction wasperformed over a 2 hour period at 50 ° C., thereby preparing the silicafilm forming materials.

The silica films of Examples 28 to 54 were manufactured by using thesilica film forming materials thus obtained in the same manner as inExample 1. Further, the characteristics of the respective silica filmswere evaluated in the same manner as in Example 1, the respectiveresults of which are shown in Tables 5 to 7 as well.

In addition, the existence of silicone polymer in the silica film thusobtained was verified by infrared spectroscopic analysis. FIG. 2 showsthe composition of the polymer in the silica film of Example 28.According to FIG. 2, the existence of CHx, Si—O—Si bond, Si—CH₃ bond,and Si—CHx- bond can be verified in the silica film of Example 28, andit can be found that the silica film of the Example 28 includes thesilicone polymer having all of these constructions.

TABLE 5 Example No. 28 29 30 31 32 33 34 35 36 1,2-DMCSE 0.1 0.1 0.10.15 0.15 0.15 0.1 0.1 0.1 (mol) 1,4-DMCSB — — — — — — — — — (mol) TCS(mol) 0.1 — — 0.05 — — 0.05 0.05 — MTCS (mol) — 0.1 — — 0.05 — 0.05 —0.05 PTCS (mol) — — 0.1 — — 0.05 — 0.05 0.05 500 ppm nitric 0.7 0.6 0.60.6 0.5 0.5 0.6 0.6 0.5 acid solution (mol) PGMEA (g) 200 200 200 200200 200 200 200 200 Dielectric 2.7 2.7 2.6 2.7 2.6 2.6 2.8 2.7 2.7constant* Moisture 2.7 2.7 2.6 2.7 2.6 2.6 2.8 2.7 2.7 resistance**Chemical −32 −16 −12 −27 −10 −14 −19 −15 −9 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:3 1:4 1:5 1:4 1:4 1:5 1:3 1:3 1:3 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 2 2 3 22 3 2 2 3 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

TABLE 6 Example No. 37 38 39 40 41 42 43 44 45 1,2-DMCSE — — — — — — — —— (mol) 1,4-DMCSB 0.1 0.1 0.1 0.15 0.15 0.15 0.1 0.1 0.1 (mol) TCS (mol)0.1 — — 0.05 — — 0.05 0.05 — MTCS (mol) — 0.1 — — 0.05 — 0.05 — 0.05PTCS (mol) — — 0.1 — — 0.05 — 0.05 0.05 500 ppm nitric 0.7 0.6 0.6 0.60.5 0.5 0.6 0.6 0.5 acid solution (mol) PGMEA (g) 200 200 200 200 200200 200 200 200 Dielectric 2.8 2.7 2.7 2.6 2.7 2.7 2.6 2.7 2.7 constant*Moisture 2.8 2.7 2.7 2.6 2.7 2.7 2.6 2.7 2.7 resistance** Chemical −25−12 −12 −19 −13 −18 −15 −15 −13 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:3 1:4 1:5 1:4 1:4 1:5 1:3 1:3 1:3 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 2 3 2 22 3 3 3 2 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

TABLE 7 Example No. 46 47 48 49 50 51 52 53 54 1,2-DMCSE 0.05 0.05 0.050.075 0.075 0.075 0.05 0.05 0.05 (mol) 1,4-DMCSB 0.05 0.05 0.05 0.0750.075 0.075 0.05 0.05 0.05 (mol) TCS (mol) 0.1 — — 0.05 — — 0.05 0.05 —MTCS (mol) — 0.1 — — 0.05 — 0.05 — 0.05 PTCS (mol) — — 0.1 — — 0.05 —0.05 0.05 500 ppm nitric 0.7 0.6 0.6 0.5 0.5 0.5 0.7 0.7 0.6 acidsolution (mol) PGMEA (g) 200 200 200 200 200 200 200 200 200 Dielectric2.7 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 constant* Moisture 2.7 2.6 2.6 2.62.6 2.6 2.6 2.6 2.6 resistance** Chemical −27 −14 −18 −24 −18 −29 −21−25 −18 resistance (nm/min)Adhesive >600 >600 >600 >600 >600 >600 >600 >600 >600 strength (kgf/mmsq.) Etching rate 1:4 1:4 1:5 1:4 1:4 1:5 1:4 1:4 1:4 ratio*** Resistform Good Good Good Good Good Good Good Good Good Etching shift 3 2 2 22 2 2 2 3 (nm) *(dielectric constant immediately after formation ofsilica film) **(dielectric constant after leaving to stand for 7 days)***(ratio of silica film to porous silica film)

From the results of tables 5 to 7, it has been found that, as the samewith the Examples 1 to 27, each silica film made by the silica filmforming materials of Examples 28 to 54 has low dielectric constant, doesnot change the dielectric constant even after seven days, has excellentmoisture resistance, chemical resistance and etching resistance (etchingrate ratio) with a small amount of etching shift, possesses resistanceto both wet and dry etching, and has good adhesive strength.

Comparative Examples 9 to 16

The silica films of Comparative Examples 9 to 16 were manufactured bypreparing the silica film forming materials in the same manner as inExample 28, except for using one of the following (a) and (b), in theamounts as shown in Table 8,

(a) 1,2-bis (dimethylchlorosilyl) ethane (1,2-DMCSE) and 1,4-bis(dimethylchlorosilyl) benzene (1,4-DMCSB), which are the siliconcompounds expressed by the structural formula (10), and

(b) at least one of tetrachlorosillan (TCS) which is the siliconcompound expressed by the structural formula (11); andmethyltrichlorosillan (MTCS) and phenyltrichlorosillan (PTCS), which arethe silicon compounds expressed by the structural formula (12), andexcept that the hydrolysis condensation polymerization reaction was notperformed. Moreover, the characteristics of the respective silica filmswere evaluated in the same manner as in Example 1. The results are alsoshown in Table 8.

In addition, the existence of silicone polymer in the silica film thusobtained was verified by infrared spectroscopic analysis. FIG. 2 showsthe composition of the polymer in the silica film of Comparative Example12. According to FIG. 2, the existence of CHx, Si—O—Si bond, Si—CH₃bond, and Si—CHx- bond cannot be verified in the silica film ofComparative Example 12, and it can be found that the silica film of theComparative Example 12 does not include the silicone polymer having allof these constructions.

TABLE 8 Comp. Example No. 9 10 11 12 13 14 15 16 1,2-DMCSE — — — — — —0.2 — (mol) 1,4-DMCSB — — — — — — — 0.2 (mol) TCS (mol) 0.2 — — 0.1 0.1— — — MTCS (mol) — 0.2 — 0.1 — 0.1 — — PTCS (mol) — — 0.2 — 0.1 0.1 — —500 ppm nitric 0.8 0.6 0.6 0.7 0.7 0.6 0.7 0.7 acid solution (mol) PGMEA(g) 200 200 200 200 200 200 200 200 Dielectric 4.8 3.3 3.2 4.1 3.4 3.42.7 2.8 constant* Moisture 5.6 3.5 3.4 4.6 3.8 3.5 3.0 3.0 resistance**Chemical −721 −436 −332 −530 −480 −392 −211 −134 resistance (nm/min)Adhesive >600 >600 520 480 440 330 260 190 strength (kgf/mm sq.) Etchingrate 1:1 1:1 1:2 1:1 1:1 1:2 1:15 1:15 ratio*** Resist form PatternPattern Good Pattern Good Good Good Good collapse collapse collapseEtching shift 18 16 8 12 10 6 Unopened Unopened (nm) *(dielectricconstant immediately after formation of silica film) **(dielectricconstant after leaving to stand for 7 days) ***(ratio of silica film toporous silica film)

From the results of table 8, it has been found that, as the same withComparative Examples 1 to 8, each silica film made by the silica filmforming materials of Comparative Examples 9 to 16 has high dielectricconstant, increases further the dielectric constant after seven days,has poor moisture resistance, chemical resistance and etching resistance(etching rate ratio) with a large amount of etching shift, possesses lowresistance to both wet and dry etching, and has low adhesive strength.

Example 55

—Manufacture of Multilayer Wiring Structure and Semiconductor Device—

The multilayer wiring structure and the semiconductor device of thepresent invention were manufactured as follows. First, as shown in FIG.1A, a transistor, which has a source diffusion layer 5 a, a draindiffusion layer 5 b, and a side wall insulation film 3 and is separatedby inter-element separation film 2, was formed on a silicon wafer 1.Then, as shown in FIG. 1B, a interlayer insulation film 6 (phosphorusglass) and a stopper film 7 (SiC) was formed on the silicon wafer 1, andthen a contact hole for extracting an electrode was formed. As shown inFIG. 1C, after forming the barrier film 8 (TiN) by way of sputtering tohave a thickness of 50 nm, a tungsten (W) conductor plug 9 (blanket) wasfilled in the contact hole by mixing WF₆ gas and hydrogen gas andperforming a reduction to form a via, and portions other than the viawas removed by way of chemical mechanical polishing (CMP).

Further, as shown in FIG. 1D, an SiC:O:H film 10 was formed to have athickness of 30 nm on the stopper film 7 on which the via has beenformed, and a porous silica film (low dielectric constant film; wiringseparation insulating film) 11 was formed thereon so as to have athickness of 160 nm, and a silica film 12 was formed on the poroussilica film, using the silica film forming material of Example 1, so asto have a thickness of 30 nm. Further, as shown in FIG. 1E, the silicafilm 12 was processed by way of the F plasma method with CF₄/CHF₃ gas asthe source material, using the resist layer as a mask having a patternof a first wiring layer with a wiring width of 100 nm and a space of 100nm, thereby forming a wiring trench. Then, as shown in FIG. 1F, abarrier film 13 (TaN) was formed in the wiring trench by way ofsputtering method to have a thickness of 10 nm to prevent the diffusionof the wiring material (copper) into the porous silica film 11. Next, aseed layer (Cu), which functions as an electrode at the time ofelectrolytic plating, was formed on the surface of the barrier film 13formed in the wiring trench, by way of sputtering method to a thicknessof 10 nm. Next, a copper wiring 14 (Cu) was deposited to have athickness of 600 nm by way of the electrolytic plating, and then thecopper was removed except for the wiring pattern portions by way ofchemical mechanical polishing (CMP). Then, a stopper film (diffusionprevention film) 15 formed of an SiC:O:H film was formed on the copperwiring 14 (Cu) to have a thickness of 30 nm, thereby forming a firstwiring layer (copper). Here, the stopper film (diffusion preventionfilm) 15 was formed by way of the plasma CVD method by using silane gasand ammonia gas to prevent the diffusion of the wiring material (copper)into the porous silica film 11.

Next, as shown in FIG. 1G, the porous silica film (low dielectricconstant film; wiring separation insulating film, SiOC film) 16 wasformed on the stopper film (diffusion prevention film) 15 to have athickness of 180 nm. Then, a silica film 17 was formed on the poroussilica film 16 to have a thickness of 30 nm by using the silica filmforming material of Example 1. Further, as shown in FIG. 1H, a poroussilica film (low dielectric constant film) 18 was formed on the silicafilm 17 to have a thickness of 160 nm, and the silica film 19 was formedso as to have a thickness of 30 nm by using the silica film formingmaterial of Example 1.

Then, as shown in FIG. 1I, a via was formed in these insulation films byusing a resist layer having a via pattern as a mask. Specifically, thesilica film 19, the porous silica film 18, the silica film 17, and theporous silica film 16 were processed in this order by way of the Fplasma method with CF₄/CHF₃ gas as the source material, and changing thegas composition and pressure. Next, a wiring trench was formed by way ofthe F plasma method using CF₄/CHF₃ gas as the source material by using aresist layer having a pattern of a second wiring layer as a mask. Then,as shown in FIG. 1J, a barrier film (TaN) 20 for preventing thediffuaion of the wiring material (copper) into the porous silica film 18was formed in the via and the wiring trench by way of sputtering methodto have a thickness of 10 nm. Next, a seed layer (Cu), which functionsas an electrode at the time of electrolytic plating, was formed to havea thickness of 10 nm on the surface of the barrier film 20 formed in thewiring trench. Next, a copper wiring 21 (Cu) was deposited by way of theelectrolytic plating method so as to be a thickness of 1,400 nm, andthen the copper was removed except for the wiring pattern portions byway of chemical mechanical polishing (CMP). Further, as shown in FIG.1K, an SiC:O:H film 22 was formed to have a thickness of 30 nm by way ofthe plasma CVD method, thereby forming a second via and wiring layer(copper).

A third via and wiring layer (copper) was formed by the same manner asin the second via and wiring layer described above, whereby asemiconductor device having a third layer copper-wiring structure, whichcorresponds to a multilayer wiring structure of the present invention,was manufactured.

In the manner described above, one million semiconductor devices havingcontinuous via in which the via and copper wiring are provided in serieswere manufactured. The yield of the continuous via was 91%. Moreover, aneffective dielectric constant was computed based on the inter-layercapacity to be 2.6. Moreover, wiring resistance was measured with aresistance measuring instrument (“HP4284A made by Agilent Technology ofUS) after leaving to stand for 3,000 hours at the high temperature of200° C., which indicated no increase in resistance.

Example 56

Multilayer wiring structure and semiconductor device of Example 56 weremanufactured by forming the silica films 12, 17 and 19 in the samemanner as in Example 55, except that the silica film forming material ofExample 1 was replaced by that of Example 28.

One million semiconductor devices of Example 56 having continuous via inwhich the via and copper wiring are provided in series weremanufactured. The yield of the continuous via was 96%. Moreover, aneffective dielectric constant was computed based on the inter-layercapacity to be 2.55. Moreover, wiring resistance was measured with aresistance measuring instrument (“HP4284A made by Agilent Technology ofUS) after leaving to stand for 3,000 hours at a high temperature of 200°C., which indicated no increase in resistance.

Comparative Example 17

Multilayer wiring structure and semiconductor device of ComparativeExample 17 were manufactured by forming the silica films 12, 17 and 19in the same manner as in Example 55, except that the silica film formingmaterial of Example 1 was replaced by that of Comparative Example 1.

One million semiconductor devices of Comparative Example 17 havingcontinuous via in which the via and copper wiring are provided in serieswere manufactured. The yield of the continuous via was 34%. Moreover, aneffective dielectric constant was computed based on the inter-layercapacity to be as high as 2.55, which is quite high. Moreover, wiringresistance was measured with a resistance measuring instrument (“HP4284Amade by Agilent Technology of US) after leaving to stand for 3,000 hoursat a high temperature of 200° C., which indicated increase inresistance.

The present invention can overcome the problems in the related art andprovide a silica film with excellent etching resistance, chemicalresistance, adhesiveness, and a low dielectric constant along with theeffective manufacturing method thereof, silica film forming materialsuitable for formation of the silica film, multilayer wiring structureenabling reduction of inter-layer parasitic capacity along with theeffective manufacturing method thereof, and a high-speed, highlyreliable semiconductor device having the silica film as an interlayerinsulation film and the like along with the effective manufacturingmethod thereof.

The silica film forming material of the present invention has excellentetching resistance, chemical resistance, moisture resistance andadhesiveness as well as a low dielectric constant. Hence, it isextremely suitable for use in an interlayer insulation film and/or aprotection film to be formed on the surface of the interlayer insulationfilm. Moreover, the silica film forming material of the presentinvention is particularly suitable for manufacturing the silica film ofthe present invention, the multilayer wiring structure of the presentinvention and the semiconductor device of the present invention.

The method of manufacturing a silica film of the present invention isextremely suitable for manufacturing various low dielectric constantfilms such as an interlayer insulation film and protection film.Moreover, the method of manufacturing a silica film of the presentinvention is particularly suitable for manufacturing the silica film ofthe present invention.

The silica film of the present invention excels in properties of etchingresistance, chemical resistance, moisture resistance, and adhesivenesswith an underlying layer, making it particularly suitable for use in asemiconductor integration circuit and the like in which a higherresponse speed is required.

The method of manufacturing a multilayer wiring structure of the presentinvention is extremely suitable for manufacturing the multilayer wiringstructure of the present invention.

The multilayer wiring structure of the present invention increasessignal transmission speed, and hence is particularly suitable for asemiconductor integration circuit and the like in which a higherresponse speed is required.

The method of manufacturing a semiconductor device of the presentinvention is suitably used for manufacturing various semiconductordevices, such as flash memories, DRAM, FRAM, and MOS transistors, andparticularly suitable for manufacting the semiconductor device of thepresent invention.

The semiconductor device of the present invention enables loweringinter-wiring parasitic capacity and wiring resistance, and has highspeed and reliability.

1. A silica film forming material, comprising a silicone polymer whichcomprises, as part of its structure, an Si—O—Si bond, an Si-CH₃ bond andan Si—CHx- bond, where x represents an integer of 0 to 2, wherein thesilicone polymer is obtained by a hydrolysis condensation polymerizationreaction of at least one silicon compound expressed by the followinggeneral formulae (1) to (3), and at least one of silicon compoundexpressed by the following general formulae (4) to (7):

where, in the general formulas (1) to (7), n represents either 0 or 1;R¹ may be the same as or different from each other, represents oneselected from the group consisting of a chlorine atom, a bromine atom, afluorine atom, and a hydrogen atom when n=0, and represents one selectedfrom the group consisting of a hydrocarbon with a carbon number of 1 to4, an aromatic hydrocarbon, a hydrogen atom and a carboxyl group whenn=1; R² represents one selected from the group consisting of ahydrocarbon with a carbon number of 1 to 4, and an aromatic hydrocarbon;and R³ may be the same as or different from each other, and representsone selected from the group consisting of a hydrocarbon with a carbonnumber of 1 to 3 and an aromatic hydrocarbon.
 2. The silica film formingmaterial according to claim 1, wherein the hydrolysis condensationpolymerization reaction is performed with a solution having a pH of 1 to11.